Sample records for manganese silicides

The Electrical Contact for Higher ManganeseSilicide Thermoelectric Material Xinghua Shi, Zahra Zamanipour, Daryoosh Vashaee Several electrical contact materials for Higher ManganeseSilicide (HMS) are introduced. HMS is useful thermoelectric material for medium to high temperature applications. We have investigated several materials including Co, Ni, Cr, Ti, Mo, MnSi, MoSi2, and TiSi2 in search of the best contact material to HMS. The low electrical resistivity and reliability of the contact are two important elements to make a high efficient TE device. Moreover, the contact must maintain its chemical, mechanical, thermal, and electrical properties over a broad range of temperature (20C-700C). The investigated elemental metals failed to make reliable contact in terms of mechanical and chemical stability at high temperature. In contrast, the investigated metal silicides showed superior stability over extended operation at high temperature. The thermal stability and strong mechanical bonding of TiSi2 C54 phase and MnSi were specially observed. Their ohmic contact resistance was also within the range of interest over the whole range of temperature (10-5 -10-4 Ω cm2) . This work was supported by AFOSR High Temperature Materials and NSF under contract CBET0933763.

Five metals with large work functions including Co, Ni, Cr, Ti, and Mo and two silicides including MnSi and TiSi2 were examined to determine the best contact material for the thermoelectric material higher manganesesilicide (HMS). Three-layer structures of HMS/contact/HMS were prepared in a sintering process. The contact resistance was measured versus temperature. The structures were subjected to x-ray diffraction and energy-dispersive x-ray spectroscopy examination. Thermal stability of the structures was determined by heating the samples to 700°C for different time intervals. The pure metals failed to make reliable contacts due to poor mechanical and chemical stability at high temperatures. In contrast, the metal silicides (MnSi and TiSi2) showed superior chemical and mechanical stability after the thermal stability test. The observed contact resistance of MnSi and TiSi2 was within the range of practical interest (10-5 Ω cm2 to 10-4 Ω cm2) over the entire range of investigated temperatures (20°C to 700°C). The best properties were found for the nanograined MnSi, for which the resistance of the contact was as low as 10-6 Ω cm2.

Comet 26P/Grigg-Skjellerup was identified as a source of an Earth-crossing dust stream with low Earth-encounter velocities, with peak anticipated fluxes during April in 2003 and 2004 [1]. In response to this prediction, NASA performed dedicated stratospheric dust collections using high altitude aircraft to target potential interplanetary dust particles (IDPs) from this comet stream in April 2003. Several IDPs from this collection have shown unusually low noble gas abundances [2] consistent with the predicted short space exposure ages of Grigg-Skjellerup dust particles [1]. High abundances of large D enrichments [3] and presolar grains [4] in IDPs from this collection are also consistent with an origin from the comet Grigg-Skjellerup. Here we report a new mineral from one of the cluster IDPs of the "Grigg-Skjellerup" collection, L2055. Our report focuses on an unusual manganese-iron-chromium silicide phase that, to our knowledge, has not been observed previously in nature. This unique phase may also shed light on the genesis of the enigmatic low-Fe,Mn-enriched (LIME) olivine that has been previously reported in IDPs and meteorites [5].

Higher manganesesilicides (HMSs, MnSi γ , γ ˜ 1.75) show promise for use as low-cost and environmentally friendly thermoelectric materials. To reduce their thermal conductivity, we partially substituted the Mn site with heavy elements using liquid quenching. Fabricated samples possess a curly ribbon-shape with about a 10- μm thickness and 1-mm width, with high surface roughness. In this study, we determined the thermal conductivity of the curly-ribbon-shaped samples using two independent methods: the 3 ω method with two heat flow models, and the steady-state method using a physical property measurement system (PPMS; Quantum Design). We succeeded in estimating the thermal conductivity at the temperature range of 100-200 K using the PPMS. The estimated thermal conductivity of non-doped HMSs shows a constant value without temperature dependence of 2.2 ± 0.8 W K-1m-1 at 100-200 K. The difference of thermal conductivities of W-doped and non-doped HMSs was not recognized within the measurement error.

Thermoelectric Power Generation (TEPG) is the most efficient and commercially deployable power generation technology for harvesting wasted heat from such things as automobile exhausts, industrial furnaces, and incinerators, and converting it into usable electrical power. We investigated the materials magnesium silicide (Mg2Si) and manganesesilicide (MnSi) for TEG. MgSi2 and MnSi are environmentally friendly, have constituent elements that are abundant in the earth's crust, non-toxic, lighter and cheaper. In Phase I, we successfully produced Mg2Si and MnSi material with good TE properties. We developed a novel technique to synthesize Mg2Si with good crystalline quality, which is normally very difficult due to high Mg vapor pressure and its corrosive nature. We produced n-type Mg2Si and p-type MnSi nanocomposite pellets using FAST. Measurements of resistivity and voltage under a temperature gradient indicated a Seebeck coefficient of roughly 120 V/K on average per leg, which is quite respectable. Results indicated however, that issues related to bonding resulted in high resistivity contacts. Determining a bonding process and bonding material that can provide ohmic contact from room temperature to the operating temperature is an essential part of successful device fabrication. Work continues in the development of a process for reproducibly obtaining low resistance electrical contacts.

The Earth accretes approximately 40,000 tons of cosmic dust annually, originating mainly from the disintegration of comets and collisions among asteroids. This cosmic dust, also known as interplanetary dust particles (IDPs), is a subject of intense interest since it is made of the original building blocks of our Solar System. Although the specific parent bodies of IDPs are unknown, the anhydrous chondritic-porous IDPs (CP-IDPs) subset has been potentially linked to a cometary source. The CP-IDPs are extremely primitive materials based on their unequilibrated mineralogy, C-rich chemistry, and anomalous isotopic signatures. In particular, some CP-IDPs escaped the thermal, aqueous and impact shock processing that has modified or destroyed the original mineralogy of meteorites. Thus, the CP-IDPs represent some of the most primitive solar system materials available for laboratory study. Most CP-IDPs are comprised of minerals that are common on Earth. However, in the course of an examination of one of the CP-IDPs, we encountered three sub-micrometer sized grains of manganesesilicide (MnSi), a phase that has heretofore not been found in nature. In the seminar, we would like to focus on IDP studies and this manganesesilicide phase that has been approved as the first new mineral identified from a comet by the International Mineralogical Association (IMA) in 2008. The mineral is named in honour of Donald E. Brownlee, an American astronomer and a founder of the field of cosmic dust research who is the principal investigator of the NASA Stardust Mission that collected dust samples from Comet 81P/Wild-2 and returned them to Earth. Much of our current view and understanding of the early solar system would not exist without the pioneering work of professor Don Brownlee in the study of IDPs.

An easy and efficient process involving ball milling under soft conditions and spark plasma sintering was used to synthesize higher manganesesilicide (HMS)-based compounds, for example MnSi1.75Ge0.02, with different molybdenum, tungsten, and aluminium substitution. The x-ray diffraction patterns of the samples after sintering showed the main phase to be HMS with the presence of some side products. Molybdenum substitution enlarges the unit cells more than tungsten substitution, owing to its greater solubility in the HMS structure, whereas substitution with aluminium did not substantially alter the cell parameters. The electrical resistivity of HMS-based compounds was reduced by <10% by this substitution, because of increased carrier concentrations. Changes of the Seebeck coefficient were insignificant after molybdenum and aluminium substitution whereas tungsten substitution slightly reduced the thermopower of the base material by approximately 8% over the whole temperature range; this was ascribed to reduced carrier mobility as a result of enhanced scattering. Substitution with any combination of two of these elements resulted in no crucial modification of the electrical properties of the base material. Large decreases of lattice thermal conductivity were observed, because of enhanced phonon scattering, with the highest reduction up to 25% for molybdenum substitution; this resulted in a 20% decrease of total thermal conductivity, which contributed to improvement of the figure of merit ZT of the HMS-based materials. The maximum ZT value was approximately 0.40 for the material with 2 at.% molybdenum substitution at the Mn sites.

We report on the thermoelectric properties of the Higher ManganeseSilicide MnSi₁.₇₅ (HMS) synthesized by means of a one-step non-equilibrium method. The ultrahigh cooling rate generated from the melt-spin technique is found to be effective in reducing second phases, which are inevitable during the traditional solid state diffusion processes. Aside from being detrimental to thermoelectric properties, second phases skew the revealing of the intrinsic properties of this class of materials, for example the optimal level of carrier concentration. With this melt-spin sample, we are able to formulate a simple model based on a single parabolic band that can well describe the carrier concentration dependence of the Seebeck coefficient and power factor of the data reported in the literature. An optimal carrier concentration around 5x10²⁰ cm⁻³ at 300 K is predicted according to this model. The phase-pure melt-spin sample shows the largest power factor at high temperature, resulting in the highest zT value among the three samples in this paper; the maximum value is superior to those reported in the literatures.

We report on the thermoelectric properties of the Higher ManganeseSilicide MnSi₁.₇₅ (HMS) synthesized by means of a one-step non-equilibrium method. The ultrahigh cooling rate generated from the melt-spin technique is found to be effective in reducing second phases, which are inevitable during the traditional solid state diffusion processes. Aside from being detrimental to thermoelectric properties, second phases skew the revealing of the intrinsic properties of this class of materials, for example the optimal level of carrier concentration. With this melt-spin sample, we are able to formulate a simple model based on a single parabolic band that can well describemore » the carrier concentration dependence of the Seebeck coefficient and power factor of the data reported in the literature. An optimal carrier concentration around 5x10²⁰ cm⁻³ at 300 K is predicted according to this model. The phase-pure melt-spin sample shows the largest power factor at high temperature, resulting in the highest zT value among the three samples in this paper; the maximum value is superior to those reported in the literatures.« less

We report on the thermoelectric properties of the higher manganesesilicide MnSi{sub 1.75} synthesized by means of a one-step non-equilibrium method. The ultrahigh cooling rate generated from the melt-spin technique is found to be effective in reducing second phases, which are inevitable during the traditional solid state diffusion processes. Aside from being detrimental to thermoelectric properties, second phases skew the revealing of the intrinsic properties of this class of materials, for example, the optimal level of carrier concentration. With this melt-spin sample, we are able to formulate a simple model based on a single parabolic band that can well describe the carrier concentration dependence of the Seebeck coefficient and power factor of the data reported in the literature. An optimal carrier concentration around 5 × 10{sup 20 }cm{sup −3} at 300 K is predicted according to this model. The phase-pure melt-spin sample shows the largest power factor at high temperature, resulting in the highest zT value among the three samples in this paper.

The present challenges in the energy crisis require finding new ways to reduce consumption of fossil fuels. Thermoelectrics can help reduce fuel consumption by producing electricity from waste heat. The higher manganesesilicides (HMS) have shown promise in this field as inexpensive, nontoxic, and highly stable p-type thermoelectric materials. One of the production techniques for HMS is mechanical alloying by ball milling. In this research the effect of the ball-milling duration and speed on the phases produced was studied. Mn and Si powders were milled at speeds of 200 RPM to 800 RPM for 1 h to 7 h. X-ray diffraction (XRD) results of the samples prepared using mechanical alloying show deterioration into the MnSi phase. The sample that underwent 5 h of milling at 800 RPM showed the greatest amount of HMS phase and was subsequently spark plasma sintered. The sample showed insufficient thermoelectric properties ( ZT ≈ 0.1 at 450°C), compared with either solid-state reaction samples showing ZT ≈ 0.4 or cast samples showing ZT ≈ 0.63 at 450°C. The reduced ZT values of the mechanically alloyed and spark-plasma-sintered samples were attributed to the high relative amount of MnSi phase. The correlation between the relative amount of MnSi and the transport properties is described in detail.

Higher manganesesilicides (HMS) made of earth-abundant and non-toxic elements are regarded as promising p-type thermoelectric materials because their complex crystal structure results in low lattice thermal conductivity. It is shown here that the already low thermal conductivity of HMS can be reduced further to approach the minimum thermal conductivity via partial substitu- tion of Mn with heavier rhenium (Re) to increase point defect scattering. The solubility limit of Re in the obtained RexMn1 xSi1.8 is determined to be about x = 0.18. Elemental inhomogeneity and the formation of ReSi1.75 inclusions with 50 200 nm size are found within the HMS matrix. It is found that the power factor does not change markedly at low Re content of x 0.04 before it drops considerably at higher Re contents. Compared to pure HMS, the reduced lattice thermal conductivity in RexMn1 xSi1.8 results in a 25% increase of the peak figure of merit ZT to reach 0.57 0.08 at 800 K for x = 0.04. The suppressed thermal conductivity in the pure RexMn1 xSi1.8 can enable further investigations of the ZT limit of this system by exploring different impurity doping strategies to optimize the carrier concentration and power factor.

Experiments and analysis have been carried out to investigate the effects of Al and (Al,Ge) doping on the microstructure and thermoelectric properties of polycrystalline higher manganesesilicide (HMS) samples, which were prepared by solid-state reaction, ball milling, and followed by spark plasma sintering. It has been found that Al doping effectively increases the hole concentration, which leads to an increase in the electrical conductivity and power factor. By introducing the second dopant Ge into Al-doped HMS, the electrical conductivity is increased, and the Seebeck coefficient is decreased as a result of further increased hole concentration. The peak power factor is found to occur at a hole concentration between 1.8 × 1021 and 2.2 × 1021 cm-3 measured at room temperature. The (Al,Ge)-doped HMS samples show lower power factors owing to their higher hole concentrations. The mobility of Mn(Al0.0035GeySi0.9965-y)1.8 with y = 0.035 varies approximately as T-3/2 above 200 K, suggesting acoustic phonon scattering is the dominant scattering mechanism. The thermal conductivity of HMS does not change appreciably by Al or (Al,Ge) doping. The maximum ZT of (Al,Ge)-doped HMS is 0.57 at 823 K, which is similar to the highest value found in the Al-doped HMS samples. The ZT values were reduced in the Mn(Al0.0035GeySi0.9965-y)1.8 samples with high Ge concentration of y = 0.025 and 0.035, because of reduced power factor. In addition, a two-band model was employed to show that the hole contribution to the thermal conductivity dominates the bipolar and electron contributions for all samples from 300 to 823 K and accounts for about 12% of the total thermal conductivity at about 800 K.

A variety of crystals contain quasi-one-dimensional substructures, which yield distinctive electronic, spintronic, optical and thermoelectric properties. There is a lack of understanding of the lattice dynamics that influences the properties of such complex crystals. Here we employ inelastic neutron scatting measurements and density functional theory calculations to show that numerous low-energy optical vibrational modes exist in higher manganesesilicides, an example of such crystals. These optical modes, including unusually low-frequency twisting motions of the Si ladders inside the Mn chimneys, provide a large phase space for scattering acoustic phonons. A hybrid phonon and diffuson model is proposed to explain the low and anisotropic thermal conductivity of higher manganesesilicides and to evaluate nanostructuring as an approach to further suppress the thermal conductivity and enhance the thermoelectric energy conversion efficiency. This discovery offers new insights into the structure-property relationships of a broad class of materials with quasi-one-dimensional substructures for various applications.

The higher manganesesilicides (HMS), represented by MnSi x ( x = 1.71 to 1.75), are promising p-type leg candidates for thermoelectric energy harvesting systems in the middle-high temperature range. They are very attractive as they could replace lead-based compounds due to their nontoxicity, low-cost starting materials, and high thermal and chemical stability. Dense pellets were obtained through direct reaction between Mn and Si powders during the spark plasma sintering process. The tetragonal HMS and cubic MnSi phase amounts and the functional properties of the material such as the Seebeck coefficient and electrical and thermal conductivity were evaluated as a function of the SPS processing conditions. The morphology, composition, and crystal structure of the samples were characterized by scanning electron microscopy, energy-dispersive x-ray spectroscopy, and x-ray diffraction analyses, respectively. Differential scanning calorimetry and thermogravimetric analysis were performed to evaluate the thermal stability of the final sintered material. A ZT value of 0.34 was obtained at 600°C for the sample sintered at 900°C and 90 MPa with 5 min holding time.

A variety of crystals contain quasi-one-dimensional substructures, which yield distinctive electronic, spintronic, optical and thermoelectric properties. There is a lack of understanding of the lattice dynamics that influences the properties of such complex crystals. Here we employ inelastic neutron scatting measurements and density functional theory calculations to show that numerous low-energy optical vibrational modes exist in higher manganesesilicides, an example of such crystals. These optical modes, including unusually low-frequency twisting motions of the Si ladders inside the Mn chimneys, provide a large phase space for scattering acoustic phonons. A hybrid phonon and diffuson model is proposed to explain themore » low and anisotropic thermal conductivity of higher manganesesilicides and to evaluate nanostructuring as an approach to further suppress the thermal conductivity and enhance the thermoelectric energy conversion efficiency. This discovery offers new insights into the structure-property relationships of a broad class of materials with quasi-one-dimensional substructures for various applications.« less

Defect manganesesilicides MnSiδ (δ ~ 1.72-1.74) belong to a large family of compounds known as Nowotny chimney-ladder (NCL) phases and are closely related to an orthorhombic NCL compound TiSi2. One interesting feature is the low lattice thermal conductivity (κL ~ 2.5 W/m K) which may be due to several reasons: Since δ doesn't exceed 1.75 in MnSiδ, a considerable concentration of random vacancies exists on the Si-sublattice and can give rise to a low thermal conductivity. In addition, as synthesized MnSiδ is a mixture of many phases including Mn4Si7, Mn11Si19,Mn15Si26 and Mn27Si47 and in all these phases, while a-lattice parameter is closely matched, the c-lattice parameter substantially varies with δ. Such a closely matched a-lattice parameter can cause lattice strain and potentially reduce κL. Ru2Si3 forms solid solutions and Cr can be substituted as much as 20% in MnSiδ. These substitutions can favorably modify the lattice strain and reduce the thermal conductivity further. Hence manganesesilicides substituted with small amounts of Cr and Ru have been synthesized. Thermoelectric properties including resistivity, Seebeck and Hall coefficients and thermal conductivity will be studied and presented. *This work was supported as part of the Center for Revolutionary Materials for Solid State Energy Conversion, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001054.

Manganese is a mineral that is found in several foods including nuts, legumes, seeds, tea, whole grains, and leafy green vegetables. It is ... manganese by mouth along with other vitamins and minerals can promote growth in children who have low ...

... no RDAs for a nutrient, the Adequate Intake (AI) is used as a guide. The AI is the estimated amount of the nutrient that ... assumed to be adequate. The daily Adequate Intake (AI) levels for manganese are: infants birth to 6 ...

Manganese ; CASRN 7439 - 96 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

The area of ceramic-silicide composites represents a merging of structural ceramics and structural silicides. Such ceramic-silicide composites can possess the desirable characteristics of both classes of compounds. Important structural ceramics are materials such as Si{sub 3}N{sub 4}, SiC, Al{sub 2}O{sub 3}, and ZrO{sub 2}, which possess covalent, ionic, or mixed covalent-ionic atomic bonding. An important structural silicide is MoSi{sub 2}, which possesses mixed covalent-metallic bonding. The arena of ceramic-silicide composites encompasses both composites where the structural silicide is the matrix and the structural ceramic is the reinforcement, and composites where the structural ceramic is the matrix and the structural silicide is the reinforcement. In the former area, MoSi{sub 2}-SiC, MoSi{sub 2}-ZrO{sub 2}, and MoSi{sub 2}-Al{sub 2}O{sub 3} composites are discussed. In the latter area, Si{sub 3}N{sub 4}-MoSi{sub 2} composites are described.

The Reduced Enrichment Research and Test Reactor Program is one element of the United States Government's nonproliferation effort. High-density, low-enrichment, aluminum-clad uranium silicide fuels may be substituted for the highly enriched aluminum-clad alloy fuels now in use. Savannah River Laboratory has performed studies which demonstrate reprocessability of spent RERTR silicide fuels at Savannah River Plant. Results of dissolution and feed preparation tests and solvent extraction processing demonstrations with both unirradiated and irradiated uranium silicide fuels are presented.

The growth, properties and applications of metal silicide nanowires (NWs) have been extensively investigated. The investigations have led to significant advance in the understanding of one-dimensional (1D) metal silicide systems. For example, CoSi is paramagnetic in bulk form, but ferromagnetic in NW geometry. In addition, the helimagnetic phase and skyrmion state in MnSi are stabilized by NW morphology. The influencing factors on the growth of silicide phase have been elucidated for Ni-Si, Pt-Si, and Mn-Si systems. Promising results were obtained for spintronics, non-volatile memories, field emitter, magnetoresistive sensor, thermoelectric generator and solar cells. However, the main thrust has been in microelectronic devices and integrated circuits. Transistors of world-record small size have been fabricated. Reconfigurable Si NW transistors, dually active Si NW transistors and circuits with equal electron and hole transport have been demonstrated. Furthermore, multifunctional devices and logic gates with undoped Si NWs were reported. It is foreseen that practical applications will be realized in the near future.

Nanomaterials, including nanowires (NWs), are a new class of materials with the potential to lead to major changes in many aspects of human society. Innumerable applications for nanomaterials are envisioned or are being realized now. However, such new functionalities are and will continue to be predicated on our ability to precisely synthesize nanomaterials, a skill yet undeveloped in a majority of chemical systems. Metal silicides are a class of refractory intermetallic compounds composed of abundant elements with widely varying properties that are currently employed in a large range of technological applications. In this thesis, I describe my exploration of metal silicide NWs, particularly those in the Mn-Si binary system, in order to develop rational synthetic strategies for accessing binary and ternary silicide NWs and characterize their potential for thermoelectric and spintronic applications. Chapter 1 develops a common set of ideas and a common language before reviewing the current "state of the art" in silicide NW synthesis, exploring a number of the mysteries still surrounding silicide NW synthesis, and presenting silicide NW applications. Chapter 2 depicts the use of Mn(CO) 5SiCl3 as the vapor phase precursor to synthesize higher manganesesilicide NWs (also known as HMS, MnSi˜1.7 MnSi2--x) for the first time, the identification of the NW subphase as Mn19Si33, and conductivity measurement on HMS NWs revealing bulk-like behavior. Chapter 3 describes employing MnCl 2 as the precursor for the first successful synthesis of MnSi NWs and transverse magnetoresistance measurements on these MnSi NWs to observe the signatures of helimagnetism in NWs for the first time. Chapter 4 is a systematic examination of silicide NW synthesis by single source precursor chemical vapor deposition, highlighting the complex interplay of substrate diffusion and vapor phase reactivity giving rise to material incorporation in silicide NWs. Chapter 5 details the direct reaction of Mn

The surface of rare-earth silicides (Er, Tb, etc.), formed by the reaction of thin-film metal layers with a silicon substrate, is typically dominated by deep penetrating, regularly shaped pits. These pits may have a detrimental effect on the electronic performance of low Schottky barrier height diodes utilizing such silicides on n-type Si. This study suggests that contamination at the metal-Si or silicide-Si interface is the primary cause of surface pitting. Surface pits may be reduced in density or eliminated entirely through either the use of Si substrate surfaces prepared under ultrahigh vacuum conditions prior to metal deposition and silicide formation or by means of ion irradiation techniques. Silicide layers formed by these techniques possess an almost planar morphology.

The crystalline silicide layers formed on (111) and (100) surfaces of Au films on various Si single-crystal substrates are studied by LEED and AES in conjunction with sputter-depth profiling as a function of annealing temperature. On the (111) surface, three basic silicide structures are obtained corresponding to layers of various thicknesses as obtained by different preparation conditions. The (100) surface shows only two different structures. None of the structures is compatible with the various bulk silicide structures deduced from X-ray diffraction. Using LEED as a criterion for the presence or absence of silicide on the surface, smaller layer thicknesses are obtained than reported previously on the basis of AES studies.

Ruthenium silicide is currently under development as a promising thermoelectric material suitable for space power applications. Key to realizing the potentially high figure of merit values of this material is the development of appropriate doping techniques. In this study, manganese and iridium have been identified as useful p- and n-type dopants, respectively. Resistivity values have been reduced by more than 3 orders of magnitude. Anomalous Hall effect results, however, complicate interpretation of some of the results and further effort is required to achieve optimum doping levels.

Methods of induction melting an ultra-low-density magnesium silicide (Mg2Si) intermetallic and its alloys and the resulting microstructure and microhardness were studied. The highest quality ingots of Mg2Si alloys were obtained by triple melting in a graphite crucible coated with boron nitride to eliminate reactivity, under overpressure of high-purity argon (1.3 X 105 Pa), at a temperature close to but not exceeding 1105 °C ± 5 °C to avoid excessive evaporation of Mg. After establishing the proper induction-melting conditions, the Mg-Si binary alloys and several Mg2Si alloys macroalloyed with 1 at. pct of Al, Ni, Co, Cu, Ag, Zn, Mn, Cr, and Fe were induction melted and, after solidification, investigated by optical microscopy and quantitative X-ray energy dispersive spectroscopy (EDS). Both the Mg-rich and Si-rich eutectic in the binary alloys exhibited a small but systematic increase in the Si content as the overall composition of the binary alloy moved closer toward the Mg2Si line compound. The Vickers microhardness (VHN) of the as-solidified Mg-rich and Si-rich eutectics in the Mg-Si binary alloys decreased with increasing Mg (decreasing Si) content in the eutectic. This behavior persisted even after annealing for 75 hours at 0.89 pct of the respective eutectic temperature. The Mg-rich eutectic in the Mg2Si + Al, Ni, Co, Cu, Ag, and Zn alloys contained sections exhibiting a different optical contrast and chemical composition than the rest of the eutectic. Some particles dispersed in the Mg2Si matrix were found in the Mg2Si + Cr, Mn, and Fe alloys. The EDS results are presented and discussed and compared with the VHN data.

This paper reviewed the recent progress in the environmental embrittlement of silicide. On the surface of silicides, the Si in the silicides such as Fe{sub 3}(Si,Al) alloy reacts with both oxygen and water vapor more easy than with iron. A molecular hydrogen mechanism of surface reaction, i.e., Si + 2H{sub 2}O = SiO{sub 2} + 2H{sub 2}, can be derived. The moisture-induced embrittlement of silicides can be considered to be an embrittlement in a localized high pressure molecular hydrogen condition. It is a kinetic hydrogen gas embrittlement. Silicides may have more severely intrinsic brittleness than iron aluminides due to their special electronic structure and bonding mechanism, leading to elucidate the role of environment on ductility with difficulty. The improvement of both the intrinsic brittleness and moisture-induced embrittlement are critical for the development of silicides.

Special technique for applying silicide coatings to refractory metal alloys improves their high-temperature protective capability. Refractory metal powders mixed with a baked-out organic binder and sintered in a vacuum produces a porous alloy layer on the surface. Exposing the layer to hot silicon converts it to a silicide.

Pre-silicide implants have been used to increase the thermal stability of nickel silicide (NiSi) and to improve device performance. This study evaluates the effect of the dose, energy and species of a pre-silicide ion implant on NiSi phase formation. The resulting silicide was evaluated using sheet resistance, scanning electron Microscope (SEM) cross-sections, and Rutherford Backscattering Spectroscopy (RBS) analysis. It was found that a high dose argon implant will completely inhibit the silicide formation.

The overall objective of this program is to develop structural silicide-based materials with optimum combinations of elevated temperature strength/creep resistance, low temperature fracture toughness, and high temperature oxidation and corrosion resistance for applications of importance to the U.S. processing industry. A further objective is to develop silicide-based prototype industrial components. The ultimate aim of the program is to work with industry to transfer the structural silicide materials technology to the private sector in order to promote international competitiveness in the area of advanced high temperature materials and important applications in major energy-intensive U.S. processing industries.

We have shown the possibility of growing thick oxide films on refractory metal silicides by plasma oxidation in the 500-900°C temperature range. Thin layers of Si-rich silicides TiSi x and WSi y ( x, y > 2) deposited onto Si or SiO 2 by cosputtering have been oxidized in and RF plasma at floating potential. The oxide growth rate, composition and thickness, and the depth distribution of cations were determined by the complementary use of nuclear reaction analysis and RBS. We have found that silicon in excess in the films diffuses through the silicide towards the surface to form a SiO 2 passivating overlayer. The Si oxide growth rate is diffusion limited, while for long treatment oxidation of the silicide itself occurs with the formation of an oxide mixture (metal oxide and SiO 2).

Diagram specifies optimum fusing time for given thicknesses of refractory metal-silicide coatings on columbium C-103 substrates. Adherence to indicated fusion times ensures consistent coatings and avoids underdiffusion and overdiffusion. Accuracy of diagram has been confirmed by tests.

In this work, the kinetics of platinum silicide formation for thin Pt films (50 nm) on monocrystalline ⟨100⟩ silicon is investigated via in situ resistance measurements under isothermal (197-275 °C) conditions. For Pt2Si diffusion limited growth was observed. For PtSi formation, however, no linear relation between silicide thickness and √t was found. PtSi growth over time could be described using the Avrami relation rendering Avrami exponent n =1.4±0.1. Additionally, an effective activation energy EA=1.7±0.1 eV was derived using the Avrami k values. The findings are important for obtaining well defined silicide films and silicide-to-silicon contacts.

The dopant (B, P, and As) redistribution in a silicide on polycrystalline silicon structure after annealing at 800 and 1000 /sup 0/C was studied. The distribution of boron was found to be quite different from these of phosphorus and arsenic. At 1000 /sup 0/C, the distribution coefficient for boron at the WSi/sub 2//polycrystalline silicon interface was found to be 2.7. The solubilities of phosphorus and arsenic in WSi/sub 2/ at 1000 /sup 0/C were estimated to be 6 x 10/sup 19/ and 1.6 x 10/sup 19/ atoms/cm/sup 3/, respectively. At 800 /sup 0/C, the diffusion coefficient for the dopants was found to be equal to, or greater than 3.3 x 10/sup -12/ cm/sup 2//s, which is at least three orders of magnitude larger than in silicon.

A method is described for forming a non-corrosive silicide coating on tantalum. The coating is made through the heating of trirhenium silicides in contact with the tantalum object to approximately 1400 deg C at which temperature trirhenium silicide decomposes into rhenium and gaseous silicons. The silicon vapor reacts with the tantalum surface to form a tantalum silicide layer approximately 10 microns thick. (AEC)

Time and temperature dependencies of nickel silicide axial growth in Si nanowires (SiNWs) were studied for a temperature range of 300-440 °C and nanowire diameters of 30-60 nm. A square root time dependence of the total silicide intrusion length was found. It was concluded that formation of nickel silicides was controlled by diffusion of Ni along the nickel silicide surface or the nickel silicide/SiO2 interface to the Si/silicide interface. Subsequent annealing cycles at different temperatures revealed Arrhenius-type behavior for the increase of the intrusion length square (ΔLn2) with an activation energy of 1.45 ± 0.11 eV. Additional and significant silicide growth during heating and cooling of the wire was taken into account by using self consistent iteration procedure for ΔLn2 calculations. The resulted activation energy agrees well with previous results.

Graphical abstract: Display Omitted Highlight: ► Nickel silicides nanowire arrays prepared by a simple in situ silicidation method. ► Phases of nickel silicides could be varied by tuning the reaction temperature. ► A growth model was proposed for the nickel silicides nanowires. ► Diffusion rates of Ni and Si play a critical role for the phase variation. -- Abstract: In this paper, we report an in situ silicidizing method to prepare nickel silicide nanowire arrays with varied structures and phases. The in situ reaction (silicidation) between Si and NiCl{sub 2} led to conversion of Si nanowires to nickel silicide nanowires. Structures and phases of the obtained nickel silicides could be varied by changing the reaction temperature. At a relatively lower temperature of 700 °C, the products are Si/NiSi core/shell nanowires or NiSi nanowires, depending on the concentration of NiCl{sub 2} solution. At a higher temperature (800 °C and 900 °C), other phases of the nickel silicides, including Ni{sub 2}Si, Ni{sub 31}Si{sub 12}, and NiSi{sub 2}, were obtained. It is proposed that the different diffusion rates of Ni and Si atoms at different temperatures played a critical role in the formation of nickel silicide nanowires with different phases.

The formation of CrSi2 by ion mixing was studied as a function of temperature, silicide thickness and irradiated interface. Samples were prepared by annealing evaporated couples of Cr on Si and Si on Cr at 450 C for short times to form Si/CrSi2/Cr sandwiches. Xenon beams with energies up to 300 keV and fluences up to 8 x 10 to the 15th per sq cm were used for mixing at temperatures between 20 and 300 C. Penetrating only the Cr/CrSi2 interface at temperatures above 150 C induces further growth of the silicide as a uniform stoichiometric layer. The growth rate does not depend on the thickness of the initially formed silicide at least up to a thickness of 150 nm. The amount of growth depends linearly on the density of energy deposited at the interface. The growth is temperature dependent with an apparent activation energy of 0.2 eV. Irradiating only through the Si/CrSi2 interface does not induce silicide growth. It is concluded that the formation of CrSi2 by ion beam mixing is an interface-limited process and that the limiting reaction occurs at the Cr/CrSi2 interface.

In our paper, we review some of the key challenges associated with the Ni silicidation process in the most recent CMOS technologies. The introduction of new materials (e.g.SiGe), and of non-planar architectures bring some important changes that require fundamental investigation from a material engineering perspective. Following a discussion of the device architecture and silicide evolution through the last CMOS generations, we focus our study on a very peculiar defect, termed NiSi-Fangs. We describe a mechanism for the defect formation, and present a detailed material analysis that supports this mechanism. We highlight some of the possible metal enrichment processes of the nickel monosilicide such as oxidation or various RIE (Reactive Ion Etching) plasma process, leading to a metal source available for defect formation. Furthermore, we investigate the NiSi formation and re-formation silicidation differences between Si and SiGe materials, and between (1 0 0) and (1 1 1) orientations. Finally, we show that the thermal budgets post silicidation can lead to the formation of NiSi-Fangs if the structure and the processes are not optimized. Beyond the understanding of the defect and the discussion on the engineering solutions used to prevent its formation, the interest of this investigation also lies in the fundamental learning within the Ni–Pt–Si–Ge system and some additional perspective on Ni-based contacts to advanced microelectronic devices.

The overall objective of this program is to develop structural silicide-based materials with optimum combinations of elevated temperature strength/creep resistance, low temperature fracture toughness, and high temperature oxidation and corrosion resistance for applications of importance to the U.S. processing industry. A further objective is to develop silicide-based prototype industrial components. The ultimate aim of the program is to work with industry to transfer the structural silicide materials technology to the private sector in order to promote international competitiveness in the area of advanced high temperature materials and important applications in major energy-intensive U.S. processing industries. The program presently has a number of developing industrial connections, including a CRADA with Schuller International Inc. targeted at the area of MoSi{sub 2}-based high temperature materials and components for fiberglass melting and processing applications. The authors are also developing an interaction with the Institute of Gas Technology (IGT) to develop silicides for high temperature radiant gas burner applications, for the glass and other industries. Current experimental emphasis is on the development and characterization of MoSi{sub 2}-Si{sub 3}N{sub 4} and MoSi{sub 2}-SiC composites, the plasma spraying of MoSi{sub 2}-based materials, and the joining of MoSi{sub 2} materials to metals.

The microwave absorption properties of Ni/(C, silicides) nanocapsules prepared by an arc discharge method have been studied. The composition and the microstructure of the Ni/(C, silicides) nanocapsules were determined by means of X-ray diffraction, X-ray photoelectric spectroscopy, and transmission electron microscope observations. Silicides, in the forms of SiOx and SiC, mainly exist in the shells of the nanocapsules and result in a large amount of defects at the ‘core/shell’ interfaces as well as in the shells. The complex permittivity and microwave absorption properties of the Ni/(C, silicides) nanocapsules are improved by the doped silicides. Compared with those of Ni/C nanocapsules, the positions of maximum absorption peaks of the Ni/(C, silicides) nanocapsules exhibit large red shifts. An electric dipole model is proposed to explain this red shift phenomenon. PMID:22548846

Calculation of the performance of fusion silicide coatings under simulated atmospheric reentry conditions to a maximum temperature of 1810 K (2800 F). Both recently developed and commercially available coatings are included. Data are presented on oxidation rate with and without intentional defecting, the influence of the coatings on the ductile-brittle bend transition temperature, and the mechanical properties. Coatings appear capable of affording protection for at least 100 simulated cycles to 2600 F and 63 cycles to 2800 F.

Raman scattering as a technique for studying the formation of tungsten silicide is presented. The tungsten silicide films have been formed by rapid thermal annealing of thin tungsten films sputter deposited on silicon substrates. The Raman data are interpreted by using data from resistivity measurements, Auger and Rutherford backscattering measurements, and scanning electron microscopy.

The present article is a review of the up-to-date state of knowledge about the oxidation of silicide in film and “bulk" forms. The oxidation of silicides is analyzed with due respect to thermodynamics but the emphasis is placed on the kinetics of the process. A distinction is made between what occurs with silicide thin films used as conductors in the electronic industry, where the silicides are always in presence of excess silicon, and in the oxidation of “bulk" silicide structural parts where this condition is not encountered. Use is made of a graphical approach that was originally used to illustrate the oxidation of Si itself. The kinetic analysis provides at least a qualitative explanation of the conditions that must be met in the electronic industry to maintain the integrity of silicide layers in oxidizing atmospheres, and of the conditions that cause the occurrence of the “pest" phenomenon in structural parts. Although attention is directed mostly to silicides, it is clear that the approach and the model used are valid for other refractory compounds, so that allusions are made also to aluminides and beryllides, etc. Marker experiments to probe the motion of atoms in the silicides during oxidation are analyzed. It is suggested that the relation between electron concentrations and oxidation rates is related to the decomposition of oxygen molecules.

The iron silicides are considered key materials for silicon integrated optoelectronic devices. This report describes the synthesis of the iron silicides starting with e-beam evaporated multilayered Fe/Si samples. Samples with two chemical wavelengths were studied upon annealing and ion beam mixing. The characterization included X-ray diffraction, CEMS and Rutherford backscattering.

Magnesium silicide-based materials are a very promising class of thermoelectric materials with excellent potential for thermoelectric waste heat recovery. For the successful application of magnesium silicide-based thermoelectric generators, the development of long-term stable contacts with low contact resistance is as important as material optimization. We have therefore studied the suitability of Ni as a contact material for magnesium silicide. Co-sintering of magnesium silicide and Ni leads to the formation of a stable reaction layer with low electrical resistance. In this paper we show that the contacts retain their low electrical contact resistance after annealing at temperatures up to 823 K for up to 168 h. By employing scanning electron microscope analysis and time-of-flight (ToF)-secondary ion mass spectrometry, we can further show that elemental diffusion is occurring to a very limited extent. This indicates long-term stability under practical operation conditions for magnesium silicide/nickel contacts.

For better oxidation resistance of refractory metals in air, the electroless coating of silicide in the molten salt was developed in open air at 973 1173 K. The molten salt consists of NaCl, KCl, Na2SiF6 and Si powder, where the proportional reaction between Si and Si4+ ions forms Si2+ ions. Si2+ deposits on the metal substrate and forms the metal silicide. The deposited silicide layers were classified into two categories depending on the metal substrates: (1) Nb, Mo and Cr mainly formed silicon-rich disilicide (MSi2) layer. (2) Fe, Ni and Co formed silicon-poor silicide layer (MSin, n<2), such as Fe3Si. This difference was described by the diffusivity of Si through the silicide layer into the metal.

A method for forming an epitaxial cobalt silicide layer on a MOS device includes sputter depositing cobalt in an ambient to form a first layer of cobalt suicide on a gate and source/drain regions of the MOS device. Subsequently, cobalt is sputter deposited again in an ambient of argon to increase the thickness of the cobalt silicide layer to a second thickness.

A titanium silicide material based on Ti.sub.5 Si.sub.3 intermetallic compound exhibits substantially improved oxidative stability at elevated temperatures. In particular, carbon is added to a Ti.sub.5 Si.sub.3 base material in an amount (e.g. about 0.3 to about 3.6 weight % C) effective to impart substantially improved oxidative stability at elevated temperatures, such as about 1000.degree. C. Boron is added to a Ti.sub.5 Si.sub.3 base material in an amount (e.g. about 0.3 to about 3.3 weight % B) to this same end.

A titanium silicide material based on Ti{sub 5}Si{sub 3} intermetallic compound exhibits substantially improved oxidative stability at elevated temperatures. In particular, carbon is added to a Ti{sub 5}Si{sub 3} base material in an amount (e.g. about 0.3 to about 3.6 weight % C) effective to impart substantially improved oxidative stability at elevated temperatures, such as about 1000 C. Boron is added to a Ti{sub 5}Si{sub 3} base material in an amount (e.g. about 0.3 to about 3.3 weight % B) to this same end. 3 figs.

A titanium silicide material based on Ti.sub.5 Si.sub.3 intermetallic compound exhibits substantially improved oxidative stability at elevated temperatures. In particular, carbon is added to a Ti.sub.5 Si.sub.3 base material in an amount (e.g. about 0.3 to about 3.6 weight % C) effective to impart substantially improved oxidative stability at elevated temperatures, such as about 1000.degree. C. Boron is added to a Ti.sub.5 Si.sub.3 base material in an amount (e.g. about 0.3 to about 3.3 weight % B) to this same end.

A titanium silicide material based on Ti{sub 5}Si{sub 3} intermetallic compound exhibits substantially improved oxidative stability at elevated temperatures. In particular, carbon is added to a Ti{sub 5}Si{sub 3} base material in an amount (e.g. about 0.3 to about 3.6 weight % C) effective to impart substantially improved oxidative stability at elevated temperatures, such as about 1000 C. Boron is added to a Ti{sub 5}Si{sub 3} base material in an amount (e.g. about 0.3 to about 3.3 weight % B) to this same end. 3 figs.

A titanium silicide material based on Ti.sub.5 Si.sub.3 intermetallic compound exhibits substantially improved oxidative stability at elevated temperatures. In particular, carbon is added to a Ti.sub.5 Si.sub.3 base material in an amount (e.g. about 0.3 to about 3.6 weight % C) effective to impart substantially improved oxidative stability at elevated temperatures, such as about 1000.degree. C. Boron is added to a Ti.sub.5 Si.sub.3 base material in an amount (e.g. about 0.3 to about 3.3 weight % B) to this same end.

A titanium silicide material based on Ti{sub 5}Si{sub 3} intermetallic compound exhibits substantially improved oxidative stability at elevated temperatures. In particular, carbon is added to a Ti{sub 5}Si{sub 3} base material in an amount (e.g. about 0.3 to about 3.6 weight % C) effective to impart substantially improved oxidative stability at elevated temperatures, such as about 1000 C. Boron is added to a Ti{sub 5}Si{sub 3} base material in an amount (e.g. about 0.3 to about 3.3 weight % B) to this same end. 3 figs.

Molybdenum disilicide (MoSi{sub 2}) is a promising candidate material for high temperature structural applications. It is a high melting point (2030 C) material with excellent oxidation resistance and a moderate density (6.24 g/cm{sup 3}). However, low toughness at low temperatures and high creep rates at elevated temperatures have hindered its commercialization in structural applications. Much effort has been invested in MoSi{sub 2} composites as alternatives to pure molybdenum disilicide for oxidizing and aggressive environments. Molybdenum disilicide-based heating elements have been used extensively in high-temperature furnaces. The low electrical resistance of silicides in combination with high thermal stability, electron-migration resistance, and excellent diffusion-barrier characteristics is important for microelectronic applications. Projected applications of MoSi{sub 2}-based materials include turbine airfoils, combustion chamber components in oxidizing environments, missile nozzles, molten metal lances, industrial gas burners, diesel engine glow plugs, and materials for glass processing. On this paper, synthesis, fabrication, and properties of the monolithic and composite molybdenum silicides are reviewed.

A boron-modified molybdenum silicide material is disclosed having the composition comprising about 80 to about 90 weight % Mo, about 10 to about 20 weight % Si, and about 0.1 to about 2 weight % B and a multiphase microstructure including Mo{sub 5}Si{sub 3} phase as at least one microstructural component effective to impart good high temperature creep resistance. The boron-modified molybdenum silicide material is fabricated into such products as electrical components, such as resistors and interconnects, that exhibit oxidation resistance to withstand high temperatures in service in air as a result of electrical power dissipation, electrical resistance heating elements that can withstand high temperatures in service in air and other oxygen-bearing atmospheres and can span greater distances than MoSi{sub 2} heating elements due to improved creep resistance, and high temperature structural members and other fabricated components that can withstand high temperatures in service in air or other oxygen-bearing atmospheres while retaining creep resistance associated with Mo{sub 5}Si{sub 3} for structural integrity. 7 figs.

A boron-modified molybdenum silicide material having the composition comprising about 80 to about 90 weight % Mo, about 10 to about 20 weight % Si, and about 0.1 to about 2 weight % B and a multiphase microstructure including Mo.sub.5 Si.sub.3 phase as at least one microstructural component effective to impart good high temperature creep resistance. The boron-modified molybdenum silicide material is fabricated into such products as electrical components, such as resistors and interconnects, that exhibit oxidation resistance to withstand high temperatures in service in air as a result of electrical power dissipation, electrical resistance heating elements that can withstand high temperatures in service in air and other oxygen-bearing atmospheres and can span greater distances than MoSi.sub.2 heating elements due to improved creep resistance, and high temperature structural members and other fabricated components that can withstand high temperatures in service in air or other oxygen-bearing atmospheres while retaining creep resistance associated with Mo.sub.5 Si.sub.3 for structural integrity.

The rhenium silicides are very attractive materials for semiconductor industry. In the Institute for Theoretical and Experimental Physics (ITEP) at the ion source test bench the research program of rhenium silicide production by ion beam implantation are going on. The investigation of silicon wafer after implantation of rhenium ion beam with different energy and with different total dose were carried out by secondary ions mass spectrometry, energy-dispersive x-ray microanalysis, and x-ray diffraction analysis. The first promising results of rhenium silicide film production by high intensity ion beam implantation are presented.

Over the last several years, uranium silicide fuels have been under development as low-enriched uranium (LEU) targets for Mo-99. The use of LEU silicide is aimed at replacing the UAl{sub x} alloy in the highly-enriched uranium dissolution process. A process to recover Mo-99 from low-enriched uranium silicide is being developed at Argonne National Laboratory. The uranium silicide is dissolved in alkaline hydrogen peroxide. Experiments performed to determine the optimum dissolution procedure are discussed, and the results of dissolving a portion of a high-burnup (>40%) U{sub 3}Si{sub 2} miniplate are presented. Future work related to Mo-99 separation and waste disposal are also discussed.

Experimental and theoretical efforts directed toward increasing thermoelectric figure of merit values by a factor of 2 or 3 have been encouraging in several respects. An accurate and detailed theoretical model developed for n-type silicon-germanium (SiGe) indicates that ZT values several times higher than currently available are expected under certain conditions. These new, high ZT materials are expected to be significantly different from SiGe, but not unreasonably so. Several promising candidate materials have been identified which may meet the conditions required by theory. One such candidate, ruthenium silicide, currently under development at JPL, has been estimated to have the potential to exhibit figure of merit values 4 times higher than conventional SiGe materials. Recent results are summarized.

Periodic multilayers of nanometric period are widely used as optical components for the X-ray and extreme UV (EUV) ranges, in X-ray space telescopes, X-ray microscopes, EUV photolithography or synchrotron beamlines for example. Their optical performances depend on the quality of the interfaces between the various layers: chemical interdiffusion or mechanical roughness shifts the application wavelength and can drastically decrease the reflectance. Since under high thermal charge interdiffusion is known to get enhanced, the study of the thermal stability of such structures is essential to understand how interfacial compounds develop. We have characterized X-ray and EUV siliconcontaining multilayers (Mo/Si, Sc/Si and Mg/SiC) as a function of the annealing temperature (up to 600°C) using two non-destructive methods. X-ray emission from the silicon atoms, describing the Si valence states, is used to determine the chemical nature of the compounds present in the interphases while X-ray reflectivity in the hard and soft X-ray ranges can be related to the optical properties. In the three cases, interfacial metallic (Mo, Sc, Mg) silicides are evidenced and the thickness of the interphase increases with the annealing temperature. For Mo/Si and Sc/Si multilayers, silicides are even present in the as-prepared multilayers. Characteristic parameters of the stacks are determined: composition of the interphases, thickness and roughness of the layers and interphases if any. Finally, we have evidenced the maximum temperature of application of these multilayers to minimize interdiffusion.

This thesis involves the investigation into the production of nanocrystalline silicide compounds by radio frequency inductively coupled plasma (RF-ICP) and mechanical milling. A system constructed which utilized a RF-ICP, a powder feed system and a condensation / collection chamber to produce nanocrystalline materials. Several silicides, such as Ti{sub 5}Si{sub 3}, Cr{sub 3}Si and MoSi{sub 2}, were fed into the plasma were they vaporized. The vaporized material then passed into a connecting chamber, where it condensed out of the vapor phase and the resulting powder was collected. Much of the work conducted was in designing and building of the systems components. This was followed by establishing the plasmas operating parameters. The material collected from the ICP chamber was then compared to material produced by mechanical milling. The material produced by both methods were characterized by x-ray diffraction, scanning and transmission-electron microscopy, and energy dispersive spectroscopy. The results indicate that it is possible to produce nanocrystalline material by mechanical milling; however, there is a significant amount of contamination from the milling ball and milling container. The results also show that the Ti{sub 5}Si{sub 3} and Cr{sub 3}Si compounds can be produced in nanocrystalline form by the ICP method. The resultant material collected from the ICP chamber following the MoSi{sub 2} run consisted of nanocrystalline Si and crystalline, Mo rich Si compound. Inductively coupled plasma - atomic emission spectroscopy (ICP-AES) was also used to observe the powders as they passed through the plasma. The resulting data indicates that each compound was vaporized and dissociated in the plasma. The following thesis describes the apparatus and experimental procedure used in producing nanocrystals.

The unique electronic and mechanical properties of metal silicide films render them interesting for advanced materials in plasmonic devices, batteries, field-emitters, thermoelectric devices, transistors, and nanoelectromechanical switches. However, enabling their use requires precisely controlling their electronic structure. Using platinum silicide (PtxSi) as a model silicide, we demonstrate that the electronic structure of PtxSi thin films (1 ≤ x ≤ 3) can be tuned between metallic and semimetallic by changing the stoichiometry. Increasing the silicon content in PtxSi decreases the carrier density according to valence band X-ray photoelectron spectroscopy and theoretical density of states (DOS) calculations. Among all PtxSi phases, Pt3Si offers the highest DOS due to the modest shift of the Pt5d manifold away from the Fermi edge by only 0.5 eV compared to Pt, rendering it promising for applications. These results, demonstrating tunability of the electronic structure of thin metal silicide films, suggest that metal silicides can be designed to achieve application-specific electronic properties. PMID:27322019

High dielectric constant materials, such as HfO{sub 2}, have been extensively studied as alternatives to SiO{sub 2} in new generations of Si based devices. Hf silicate/silicide formation has been reported in almost all literature studies of Hf based oxides on Si, using different methods of preparation. A silicate interface resembles close to the traditional Si/SiO{sub 2}. The silicate very likely forms a very sharp interface between the Si substrate and the metal oxide, and would be suitable for device applications. However, the thermal instability of the interfacial silicate/oxide film leads to silicidation, causing a dramatic loss of the gate oxide integrity. Despite the importance of the Hf silicide surface and interface with Si, only a few studies of this surface are present in the literature, and a structural determination of the surface has not been reported. This paper reports a study of the Hf silicide formation upon annealing by using a combination of XPS, LEED, and x-ray photoelectron diffraction (XPD) analyses. Our results clearly indicate the formation of a unique ordered Hf silicide phase (HfSi{sub 2}), which starts to crystallize when the annealing temperature is higher than 550 deg. C.

Nickel silicide Schottky diodes formed on polycrystalline Si 〈P〉 films are proposed as temperature sensors of monolithic uncooled microbolometer infrared focal plane arrays. The structure and composition of nickel silicide/polycrystalline silicon films synthesized in a low-temperature process are examined by means of transmission electron microscopy. The Ni silicide is identified as a multi-phase compound composed of 20% to 40% of Ni3Si, 30% to 60% of Ni2Si, and 10% to 30% of NiSi with probable minor content of NiSi2 at the silicide/poly-Si interface. Rectification ratios of the Schottky diodes vary from about 100 to about 20 for the temperature increasing from 22â„ƒ to 70â„ƒ; they exceed 1,000 at 80 K. A barrier of around 0.95 eV is found to control the photovoltage spectra at room temperature. A set of barriers is observed in photo-electromotive force spectra at 80 K and attributed to the Ni silicide/poly-Si interface. Absolute values of temperature coefficients of voltage and current are found to vary from 0.3%â„ƒ to 0.6%/â„ƒ for forward bias and around 2.5%/â„ƒ for reverse bias of the diodes. PMID:23594606

Discovery of superconductivity in PbO-type FeSe has generated a lot of interest. Among the samples we synthesize with similar structure, NiSi has showed anomalous but very interesting results. Nickel silicides are important electronic materials that have been used as contacts for field effect transistors, as interconnects and in nanoelectronic devices. The magnetic properties of NiSi are not well known, however. In this presentation, we report a highly unusual magnetic phenomenon in NiSi. The ac susceptibility measurements on NiSi reveal strong frequency dependence of static and dynamic susceptibilities that are primarily diamagnetic at room temperature. The static susceptibility is found to exhibit a strong frequency dependence of the diamagnetic response below 100K, while dynamic susceptibility showed peak type feature at 10KHz frequency around 50K. Detailed neutron scattering measurements on high quality powder sample of NiSi on SPINS cold spectrometer further revealed an inelastic peak around 1.5meV, even though no magnetic order is detected. The inelastic peak dissipates above 100K, which is where the static susceptibility starts to diverge with frequency. Research is supported by U.S. Department of Energy, Office of Basic Energy Sciences under Grant No. DE-SC0014461.

Traditional silicon germanium high temperature thermoelectrics have potential for improvements in figure of merit via nano-structuring with a silicide phase. A second phase of nano-sized silicides can theoretically reduce the lattice component of thermal conductivity without significantly reducing the electrical conductivity. However, experimentally achieving such improvements in line with the theory is complicated by factors such as control of silicide size during sintering, dopant segregation, matrix homogeneity, and sintering kinetics. Samples are prepared using powder metallurgy techniques; including mechanochemical alloying via ball milling and spark plasma sintering for densification. In addition to microstructural development, thermal stability of thermoelectric transport properties are reported, as well as couple and device level characterization.

The formation of cobalt silicides by arsenic ion implantation through a cobalt film which causes a mixing of the metal with the silicon substrate was investigated. Furthermore, cobalt suicides were formed by rapid thermal annealing (RTA). Sheet resistance and silicide phases of implanted Co/Si samples depend on the As dose. Ion beam mixing at doses higher than 5 × 10 15 cm -2 and RTA at temperatures T ⩾ 900° C result in almost equal values of Rs. RBS and XRD spectra of these samples illustrate the formation of a homogeneous CoSi 2 layer. Significant lateral growth of cobalt silicide beyond the edge of patterned SiO 2 was observed in samples which were only subjected to an RTA process ( T ⩾ 900 ° C), while this lateral suicide growth could be reduced efficiently by As implantation prior to RTA.

Pyramidal structural defects, 5-8μm wide, have been discovered in thin films of epitaxial ErSi2-x formed by annealing thin Er films on Si(001) substrates at temperatures of 500-800°C. The formation of these defects is not due to oxidation. We propose that they form as a result of the separation of the silicide film from the substrate and its buckling in order to relieve the compressive, biaxial epitaxial stresses. Silicon can then diffuse through the silicide or along the interface to fully or partially fill the void between the buckled erbium disilicide film and the substrate.

Iron silicide samples were grown on Si (111) substrates by solid phase epitaxy and reactive deposition epitaxy. The different iron silicide phases and their correlations with the growth parameters were analyzed by x-ray photoelectron spectroscopy, conversion electron Moessbauer spectroscopy, x-ray diffraction, atomic force microscopy, and magnetic force microscopy. The authors investigated the potential of each technique for identifying and quantifying of the phases. In particular, the authors used a semiquantitative analysis of magnetic force microscopy images to spatially resolve the semiconductor {beta}-FeSi{sub 2} phase.

A manganese vapor laser utilizing manganese chloride as a lasant has been observed and investigated. Lasing is attained by means of two consecutive electrical discharges. The maximum laser output is obtained at a vapor pressure of about 3 torr, a temperature of 680 C, and a time delay between electrical discharges of 150 microsec. The maximum energy density is 1.3 microjoule per cu cm.

Batch tests of manganese imprinted polymers of variable composition to assess their ability to extract lithium and manganese from synthetic brines at T=45C . Data on manganese uptake for two consecutive cycles are included.

Silicide Schottky contacts can be as large as 0.955 eV (E{sub v} + 0.165 eV) on n-type silicon and as large as 1.05 eV (E{sub c} {minus} 0.07 eV) on p-type silicon. Current models of Schottky barrier formation do not provide a satisfactory explanation of occurrence of this wide variation. A model for understanding Schottky contacts via screened pinning at defect levels is presented. In the present paper it is shown that most transition metal silicides are pinned approximately 0.48 eV above the valence band by interstitial Si clusters. Rare earth disilicides pin close to the divacancy acceptor level 0.41 eV below the conduction band edge while high work function silicides of Ir and Pt pin close to the divacancy donor level 0.21 eV above the valence band edge. Selection of a particular defect pinning level depends strongly on the relative positions of the silicide work function and the defect energy level on an absolute energy scale.

We compare aluminide and alumino-silicide composite coatings on niobium using halide activated pack cementation (HAPC) technique for improving its oxidation resistance. The coated samples are characterized by SEM, EDS, EPMA and hardness measurements. We observe formation of NbAl3 in aluminide coating of Nb, though the alumino-silicide coating leads to formation primarily of NbSi2 in the inner layer and a ternary compound of Nb-Si-Al in the outer layer, as reported earlier (Majumdar et al. [11]). Formation of niobium silicide is preferred over niobium aluminide during alumino-silicide coating experiments, indicating Si is more strongly bonded to Nb than Al, although equivalent quantities of aluminium and silicon powders were used in the pack chemistry. We also employ first-principles density functional pseudopotential-based calculations to calculate the relative stability of these intermediate phases and the adhesion strength of the Al/Nb and Si/Nb interfaces. NbSi2 exhibits much stronger covalent character as compared to NbAl3. The ideal work of adhesion for the relaxed Al/Nb and Si/Nb interfaces are calculated to be 3226 mJ/m2 and 3545 mJ/m2, respectively, indicating stronger Nb-Si bonding across the interface.

Metal silicides have been used in silicon technology as contacts to achieve high device performance and desired device functions. The growth and applications of silicide materials have recently attracted increasing interest for nanoscale device applications. Nanoscale silicide materials have been demonstrated with various synthetic approaches. Solid state reaction wherein high quality silicides form through diffusion of metal atoms into silicon nano-templates and the subsequent phase transformation caught significant attention for the fabrication of nanoscale Si devices. Very interestingly, studies on the diffusion and phase transformation processes at nanoscale have indicated possible deviations from the bulk and the thin film system. Here we studied growth kinetics, electronic properties and device applications of nanoscale silicides formed through solid state reaction. We have grown single crystal PtSi nanowires and PtSi/Si/PtSi nanowire heterostructures through solid state reaction. TEM studies show that the heterostructures have atomically sharp interfaces free of defects. Electrical measurement of PtSi nanowires shows a low resistivity of ˜28.6 μΩ·cm and a high breakdown current density beyond 108 A/cm2. Furthermore, using single-crystal PtSi/Si/PtSi nanowire heterostructures with atomically clean interfaces, we have fabricated p-channel enhancement mode transistors with the best reported performance for intrinsic silicon nanowires to date. In our results, silicide can provide a clean and no Fermi level pinning interface and then silicide can form Ohmic-contact behavior by replacing the source/drain metal with PtSi. It has been proven by our experiment by contacting PtSi with intrinsic Si nanowires (no extrinsic doping) to achieve high performance p-channel device. By utilizing the same approach, single crystal MnSi nanowires and MnSi/Si/MnSi nanowire heterojunction with atomically sharp interfaces can also been grown. Electrical transport studies on Mn

The biological effects of manganese were studied in a town on the coast of Dalmatia in which a ferromanganese plant has been operating since before World War II. The study focused on the question of whether the exposure to manganese can cause a higher incidence of respiratory dis...

Ti-based silicide quantum dot superlattices (QDSLs) are grown by reduced-pressure chemical vapor deposition. They are made of titanium-based silicide nanodots scattered in an n-doped SiGe matrix. This is the first time that such nanostructured materials have been grown in both monocrystalline and polycrystalline QDSLs. We studied their crystallographic structures and chemical properties, as well as the size and the density of the quantum dots. The thermoelectric properties of the QDSLs are measured and compared to equivalent SiGe thin films to evaluate the influence of the nanodots. Our studies revealed an increase in their thermoelectric properties-specifically, up to a trifold increase in the power factor, with a decrease in the thermal conductivity-making them very good candidates for further thermoelectric applications in cooling or energy-harvesting fields. PMID:26086207

This paper addresses fuel cycle cost comparisons for a generic 10 MW reactor with HEU aluminide fuel and with LEU oxide and silicide fuels in several fuel element geometries. The intention of this study is to provide a consistent assessment of various design options from a cost point of view. Fuel cycle cost benefits could result if a number of reactors were to utilize fuel elements with the same number or different numbers of the same standard fuel plate. Data are presented to quantify these potential cost benefits. This analysis shows that there are a number of fuel element designs using LEU oxide or silicide fuels that have either the same or lower total fuel cycle costs than the HEU design. Use of these fuels with the uranium densities considered requires that they are successfully demonstrated and licensed.

We report the formation of very uniform and smooth Ni(Pt)Si on epitaxially grown SiGe using Si gas cluster ion beam treatment after metal-rich silicide formation. The gas cluster ion implantation process was optimized to infuse Si into the metal-rich silicide layer and lowered the NiSi nucleation temperature significantly according to in situ X-ray diffraction measurements. This novel method which leads to more uniform films can also be used to control silicide depth in ultra-shallow junctions, especially for high Ge containing devices, where silicidation is problematic as it leads to much rougher interfaces.

A preliminary study on arc-melted samples has indicated that ruthenium silicide has the potential to obtain figure-of-merit values four times higher than that of conventional silicon-germanium material. In order to realize the high figure-of-merit values, high-quality crystal from the melt is needed. A Bridgman-like method has been employed and has realized much better crystals than arc-melted ones.

Niobium was deposited by physical vapor deposition (PVD) using e-beam evaporation on bare (100) silicon substrates and SiO2 surfaces. The formation of niobium silicide was investigated by annealing PVD Nb films in the temperatures range 400–1000°C. At all elevated annealing temperatures the resistivity of Nb silicide is substantially higher than that of Nb. The Nb silicidation as a function of temperature has been investigated and different NbXSiy compounds have been characterized. It has been observed that the annealing of the Nb film on Si is accompanied by a strong volume expansion of about 2.5 of the resulting reacted film. The films' structural properties were studied using X-Ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), and atomic force microscopy (AFM), which was not previously presented in the context of the extant NbSi literature. The X-Ray diffraction characterization of the Nb on Si sample annealed at 1000°C, showed the presence of hexagonal Nb5Si3 phases, with a dominant peak at the (200) plane, and NbSi2 phases. Fractal dimension calculations indicate a distinct transition from Stranski-Krastanov to Volmer-Weber film growth for NbSi formation at the annealing temperature of 600°C and above.

Metal silicides have been used in silicon technology as contacts to achieve high device performance and desired device functions. The growth and applications of silicide materials have recently attracted increasing interest for nanoscale device applications. Nanoscale silicide materials have been demonstrated with various synthetic approaches. Solid state reaction wherein high quality silicides form through diffusion of metal atoms into silicon nano-templates and the subsequent phase transformation caught significant attention for the fabrication of nanoscale Si devices. Very interestingly, studies on the diffusion and phase transformation processes at nanoscale have indicated possible deviations from the bulk and the thin film system. Here we studied growth kinetics, electronic properties and device applications of nanoscale silicides formed through solid state reaction. We have grown single crystal PtSi nanowires and PtSi/Si/PtSi nanowire heterostructures through solid state reaction. TEM studies show that the heterostructures have atomically sharp interfaces free of defects. Electrical measurement of PtSi nanowires shows a low resistivity of ˜28.6 μΩ·cm and a high breakdown current density beyond 108 A/cm2. Furthermore, using single-crystal PtSi/Si/PtSi nanowire heterostructures with atomically clean interfaces, we have fabricated p-channel enhancement mode transistors with the best reported performance for intrinsic silicon nanowires to date. In our results, silicide can provide a clean and no Fermi level pinning interface and then silicide can form Ohmic-contact behavior by replacing the source/drain metal with PtSi. It has been proven by our experiment by contacting PtSi with intrinsic Si nanowires (no extrinsic doping) to achieve high performance p-channel device. By utilizing the same approach, single crystal MnSi nanowires and MnSi/Si/MnSi nanowire heterojunction with atomically sharp interfaces can also been grown. Electrical transport studies on Mn

Multiphase Mo silicide alloys containing T2 (Mo{sub 5}SiB{sub 2}), Mo{sub 3}Si and Mo phases where prepared by both melting and casting (M and C) and powder metallurgical (PM) processes. Glassy phases are observed in PM materials but not in M and C materials. Microstructural studies indicate that the primary phase is Mo-rich solid solution in alloys containing {le}(9.4Si+13.8B, at. %) and T2 in alloys with {ge}(9.8Si+14.6B). An eutectic composition is estimated to be close to Mo-9.6Si-14.2B. The mechanical properties of multiphase silicide alloys were determined by hardness, tensile and bending tests at room temperature. The multiphase alloy MSB-18 (Mo-9.4Si-13.8B) possesses a flexure strength distinctly higher than that of MoSi{sub 2} and other Mo{sub 5}Si{sub 3} silicide alloys containing no Mo particles. Also, MSB-18 is tougher than MoSi{sub 2} by a factor of 4.

Multiphase Mo silicide alloys containing T2 (Mo{sub 5}SiB{sub 2}), Mo{sub 3}Si and Mo phases were prepared by both melting and casting (M and C) and powder metallurgical (PM) processes. Glassy phases are observed in PM materials but not in M and C materials. Microstructural studies indicate that the primary phase is Mo-rich solid solution in alloys containing {le}(9.4Si+13.8B, at.%) and T2 in alloys with {ge}(9.8Si+14.6B). An eutectic composition is estimated to be close to Mo-9.6Si-14.2B. The mechanical properties of multiphase silicide alloys were determined by hardness, tensile and bending tests at room temperature. The multiphase alloy MSB-18 (Mo-9.4Si-13.8B) possesses a flexure strength distinctly higher than that of MoSi{sub 2} and other Mo{sub 5}Si{sub 3} silicide alloys containing no Mo particles. Also, MSB-18 is tougher than MoSi{sub 2} by a factor of 4.

The vanadium silicide system has been found to be of increasing interest because one of the silicide phases viz. V 3Si with the A-15 structure is often accompanied by a high temperature superconductivity. We have studied the formation of vanadium silicide layers by high dose ion implantation. 30 keV 51V + ions were implanted at room temperature onto thermally evaporated a-Si films on thermally grown SiO 2 substrates. The samples were annealed in vacuum to study the possible evolution of V-Si phases. Both Seeman-Bohlin X-ray diffraction and Auger/sputter profiling techniques were used to analyse these samples. The observed Auger depth profile of the annealed samples shows a more uniform vanadium distribution as compared to the vanadium distribution in as-implanted samples, along with the changes in the Si L 2,3VV lineshape. The X-ray diffraction results show the formation of V 3Si, V 5Si 3 and VSi 2 phases. After annealing the sample in vacuum, a more ordered growth of V 3Si phase is found to be accompanied by an increase in VSi 2 phase. This has been related to the possible changes ocurring in the a-Si layers due to annealing of the sample.

Manganese is a metal that has been known named a Greek word "Magnesia" meaning magnesia nigra from Roman Empire. Manganese provide the wide range of metablic function and the multiple abnomalities from its deficiency or toxicity. In 1931, the essentiality of manganese was demonstrated with the authoritative poor growth and declined reproduction in its deficiency. Manganese deficiency has been recognized in a number of species and its signs are impaired growth, impaired reproduction, ataxia, skeletal abnormalities and disorders in lipid and carbohydrate metabolism. Manganese toxicity is also acknowledged as health hazard for animals and humans. Here manganese nutrition, metabolism and metabolic function are summarized. PMID:27455810

The synthesis of metal silicide at the metal/silicon oxide interface by electronic excitation was investigated using transmission electron microscopy. A platinum silicide, α-Pt{sub 2}Si, was successfully formed at the platinum/silicon oxide interface under 25–200 keV electron irradiation. This is of interest since any platinum silicide was not formed at the platinum/silicon oxide interface by simple thermal annealing under no-electron-irradiation conditions. From the electron energy dependence of the cross section for the initiation of the silicide formation, it is clarified that the silicide formation under electron irradiation was not due to a knock-on atom-displacement process, but a process induced by electronic excitation. It is suggested that a mechanism related to the Knotek and Feibelman mechanism may play an important role in silicide formation within the solid. Similar silicide formation was also observed at the palladium/silicon oxide and nickel/silicon oxide interfaces, indicating a wide generality of the silicide formation by electronic excitation.

A method of forming a titanium silicide (69) includes the steps of forming a transistor having a source region (58), a drain region (60) and a gate structure (56) and forming a titanium layer (66) over the transistor. A first anneal is performed with a laser anneal at an energy level that causes the titanium layer (66) to react with the gate structure (56) to form a high resistivity titanium silicide phase (68) having substantially small grain sizes. The unreacted portions of the titanium layer (66) are removed and a second anneal is performed, thereby causing the high resistivity titanium silicide phase (68) to convert to a low resistivity titanium silicide phase (69). The small grain sizes obtained by the first anneal allow low resistivity titanium silicide phase (69) to be achieved at device geometries less than about 0.25 micron.

Manganese deposits in water distribution systems accumulate metals, radionuclides and oxyanions by a combination of surface complexation, adsorption and solid substitution, as well as a combination of oxidation followed by manganese reduction and sorption of the oxidized constitu...

We report a detailed investigation of the precipitation behavior of gold in float-zone silicon from a highly supersaturated solution. Nucleation, morphology, and crystallography as well as the decomposition of the solution were examined using high-resolution electron microscopy, selected area diffraction combined with tilting experiments, Hall-effect measurements, and energy dispersive x-ray spectroscopy. After in-diffusion of gold at 1275 {degree}C annealing experiments were performed at 850 {degree}C for durations ranging from 5 min up to 35 d. It is shown that gold precipitates in small spherical particles (diameter: 10--20 nm) consisting of a metastable gold silicide. By means of selected area diffraction combined with a special tilting procedure, the unit cell is proved to be orthorhombic with lattice parameters {ital a}=0.971 nm, {ital b}=0.768 nm, and {ital c}=0.703 nm. Systematic absence of reflections in several precipitate zone-axis patterns reveals the space group of the silicide to be {ital Pnma} or {ital Pn}2{sub 1}{ital a}. According to Hall-effect measurements the concentration of substitutional gold decreases to a few percent within 5 min annealing at 850 {degree}C. Only a part of it has precipitated in gold silicide particles, which are found at small extrinsic stacking faults. The stacking faults represent a density of self-interstitials Si{sub {ital i}} of about 10{sup 18} cm{sup {minus}3}, which according to control experiments is about a factor of 50 above the equilibrium concentration of Si{sub {ital i}} at 1274 {degree}C. As annealing proceeds the stacking faults disappear, and gold is finally found in spherical particles embedded stress-free into the silicon matrix.

Biomining comprises of processing and extraction of metal from their ores and concentrates using microbial techniques. Currently this is used by the mining industry to extract copper, uranium and gold from low grade ores but not for low grade manganese ore in industrial scale. The study of microbial genomes, metabolites and regulatory pathways provide novel insights to the metabolism of bioleaching microorganisms and their synergistic action during bioleaching operations. This will promote understanding of the universal regulatory responses that the biomining microbial community uses to adapt to their changing environment leading to high metal recovery. Possibility exists of findings ways to imitate the entire process during industrial manganese biomining endeavor. This paper reviews the current status of manganese biomining research operations around the world, identifies factors that drive the selection of biomining as a processing technology, describes challenges in exploiting these innovations, and concludes with a discussion of Mn biomining's future. PMID:21632238

Silicene has emerged as the next two-dimensional material possessing a Dirac type electronic structure making it a prime candidate for integration in electronic devices. The study of silicene is relatively new and many aspects have yet to be fully understood. Here we present a scanning tunneling microscopy (STM) study of a Silicene-type surface reconstruction observed on nanometer scale hexagonal-MoSi2 crystallites. This surface reconstruction is specific to the C40 structure of h-MoSi2 and can initially be defined as a geometric silicene while the coupling between the silicene surface and the silicide bulk is under investigation. The lateral dimensions correspond to a superstructure where the silicene hexagons are slightly buckled and two of the six Si atoms are visible in the STM images creating a honeycomb pattern. The local electronic structure of the silicene is currently being studied with ST spectroscopy and the impact of confinement will be addressed. These results open an alternative route to Silicene growth by using surface reconstructions on metallic and semiconducting C40 silicide structures, which is promising for direct device integration on Si-platforms.

Ultrathin metallic silicide nanowires with extremely high aspect ratios can be easily grown, e.g., by deposition of rare earth elements on semiconducting surfaces. These wires play a pivotal role in fundamental research and open intriguing perspectives for CMOS applications. However, the electronic properties of these one-dimensional systems are extremely sensitive to atomic-sized defects, which easily alter the transport characteristics. In this study, we characterized comprehensively TbSi2 wires grown on Si(100) and correlated details of the atomic structure with their electrical resistivities. Scanning tunneling microscopy (STM) as well as all transport experiments were performed in situ using a four-tip STM system. The measurements are complemented by local spectroscopy and density functional theory revealing that the silicide wires are electronically decoupled from the Si template. On the basis of a quasiclassical transport model, the size effect found for the resistivity is quantitatively explained in terms of bulk and surface transport channels considering details of atomic-scale roughness. Regarding future applications the full wealth of these robust nanostructures will emerge only if wires with truly atomically sharp interfaces can be reliably grown.

The objective of this project was twofold. The first objective was to characterize the Hughes Aircraft Company CRC-365 platinum silicide imaging device in a starting infrared sensor system. The CRC-365 is a hybrid 256 x 256 IR focal plane array that operates in the 3-5 micrometer thermal infrared band. A complete sensor and computer interface were built for these tests, using, plans provided by the Rome Laboratory at Hanscom AFB. Testing of the device revealed largely satisfactory performance, with notable exception in the areas of temporal response, temporal noise, and electrical crosstalk. The second objective of this research was to advance the understanding of how detector nonuniformity effects reduce the performance of sensors of this type. Notable accomplishments in this area included a complete linear analysis of corrected thermal imaging in platinum silicide sensors, a nonlinear analysis of the CRC-365's expected performance, analysis of its actual performance when operated with nonuniformity correction, and the development of a new figure of merit. It was demonstrated that the CRC-365 is capable of maintaining background-noise-limited performance over at least a 40 K target temperature range, when operated with two-point nonuniformity correction.

This paper presents the growth of doped monocrystalline molybdenum-silicide-based quantum dot superlattices (QDSL). This is the first time that such nanostructured materials integrating molybdenum silicide nanodots have been grown. QDSL are grown by reduced pressure chemical vapor deposition (RPCVD). We present here their crystallographic structures and chemical properties, as well as the influence of the nanostructuration on their thermal and electrical properties. Particularly, it will be shown some specific characteristics for these QDSL, such as a localization of nanodots between the layers, unlike other silicide based QDSL, an accumulation of doping atoms near the nanodots, and a strong decrease of the thermal conductivity obtained thanks to the nanostructuration.

This letter reports on conformal formation of ultrathin Ni-silicide films over a three-dimension structure relevant to the most advanced tri-gate transistor architecture. This is achieved by combining ionization of the sputtered Ni atoms with application of an appropriate bias to the Si substrate during the sputter-deposition of Ni films. In comparison, use of ordinary DC sputtering for Ni deposition results in thinner or less uniform silicide films on the vertical sidewalls than on the top surface of the three-dimensional structure. The roughened Si sidewall surface is ascribed to be responsible for a deteriorated thermal stability of the resultant silicide films.

Manganese could easily be considered an abundant element in the Martian regolith, assuming that the composition of martian meteorites reflects the composition of the planet. Mineralogical analyses of 5 SNC meteorites have revealed an average manganese oxide concentration of 0.48%, relative to the 0.1% concentration of manganese found in the Earth's crust. On the Earth, the accumulation of manganese oxides in oceans, soils, rocks, sedimentary ores, fresh water systems, and hydrothermal vents can be largely attributed to microbial activity. Manganese is also a required trace nutrient for most life forms and participates in many critical enzymatic reactions such as photosynthesis. The wide-spread process of bacterial manganese cycling on Earth suggests that manganese is an important element to both geology and biology. Furthermore, there is evidence that bacteria can be fossilized within manganese ores, implying that manganese beds may be good repositories for preserved biomarkers. A particular genus of bacteria, known historically as Metallogenium, can form star-shaped manganese oxide minerals (called metallogenium) through the action of manganese oxide precipitation along its surface. Fossilized structures that resemble metallogenium have been found in Precambrian sedimentary formations and in Cretaceous-Paleogene cherts. The Cretaceous-Paleogene formations are highly enriched in manganese and have concentrations of trace elements (Fe, Zn, Cu, and Co) similar to modern-day manganese oxide deposits in marine environments. The appearance of metallogenium-like fossils associated with manganese deposits suggests that bacteria may be preserved within the minerals that they form. Additional information is contained in the original extended abstract.

The unique properties of graphene have raised high expectations regarding its application in carbon-based nanoscale devices that could complement or replace traditional silicon technology. This gave rise to the vast amount of researches on how to fabricate high-quality graphene and graphene nanocomposites that is currently going on. Here we show that graphene can be successfully integrated with the established metal-silicide technology. Starting from thin monocrystalline films of nickel, cobalt and iron, we were able to form metal silicides of high quality with a variety of stoichiometries under a Chemical Vapor Deposition grown graphene layer. These graphene-capped silicides are reliably protected against oxidation and can cover a wide range of electronic materials/device applications. Most importantly, the coupling between the graphene layer and the silicides is rather weak and the properties of quasi-freestanding graphene are widely preserved. PMID:23835625

A 25% reduction in NMOS contact resistance (Rc) was achieved by Selenium implantation into NiPt silicide film in VIISta Trident high-current single-wafer implanter. The Trident implanter is designed for shallow high-dose implants with high beam currents to maintain high throughput (for low CoO), with improved micro-uniformity and no energy contamination. The integration of Se implant was realized using a test chip dedicated to investigating silicide/junction related electrical properties and testable after silicidation. The silicide module processes were optimized, including the pre-clean (prior to RF PVD NiPt dep) and pre- and post-implant anneals. A 270°C soak anneal was used for RTP1, whereas a msec laser anneal was employed for RTP2 with sufficient process window (800-850°C), while maintaining excellent junction characteristics without Rs degradation.

We examine nickel silicide as a viable ohmic contact metallization for low-temperature, low-magnetic-field transport measurements of atomic-scale devices in silicon. In particular, we compare a nickel silicide metallization with aluminium, a common ohmic contact for silicon devices. Nickel silicide can be formed at the low temperatures (<400°C) required for maintaining atomic precision placement in donor-based devices, and it avoids the complications found with aluminium contacts which become superconducting at cryogenic measurement temperatures. Importantly, we show that the use of nickel silicide as an ohmic contact at low temperatures does not affect the thermal equilibration of carriers nor contribute to hysteresis in a magnetic field. PMID:21968083

We demonstrate a top-down method for fabricating nickel mono-silicide (NiSi) nanolines (also referred to as nanowires) with smooth sidewalls and line widths down to 15 nm. Four-probe electrical measurements reveal that the room temperature electrical resistivity of the NiSi nanolines remains constant as the line widths are reduced to 23 nm. The resistivity at cryogenic temperatures is found to increase with decreasing line width. This finding can be attributed to electron scattering at the sidewalls and is used to deduce an electron mean free path of 6.3 nm for NiSi at room temperature. The results suggest that NiSi nanolines with smooth sidewalls are able to meet the requirements for implementation at the 22 nm technology node without degradation of device performance. PMID:19417448

The capping of Tb and Dy silicide nanowires grown on Si(001) was studied using scanning tunneling microscopy and cross-sectional high-resolution transmission electron microscopy. Several nanometers thick amorphous Si films deposited at room temperature allow an even capping, while the nanowires maintain their original structural properties. Subsequent recrystallization by thermal annealing leads to more compact nanowire structures and to troughs in the Si layer above the nanowires, which may even reach down to the nanowires in the case of thin Si films, as well as to V-shaped stacking faults forming along {111} lattice planes. This behavior is related to strain due to the lattice mismatch between the Si overlayer and the nanowires.

While developing KMRR fuel fabrication technology an atomizing technique has been applied in order to eliminate the difficulties relating to the tough property of U{sub 3}Si and to take advantage of the rapid solidification effect of atomization. The comparison between the conventionally comminuted powder dispersion fuel and the atomized powder dispersion fuel has been made. As the result, the processes, uranium silicide powdering and heat treatment for U{sub 3}Si transformation, become simplified. The workability, the thermal conductivity and the thermal compatibility of fuel meat have been investigated and found to be improved due to the spherical shape of atomized powder. In this presentation the overall developments of atomized U{sub 3}Si dispersion fuel and the planned activities for applying the atomizing technique to the real fuel fabrication are described.

The solid state reaction between copper and silicon has been studied using Rutherford backscattering, glancing-angle x-ray diffraction, scanning electron microscopy, and x-ray photoemission spectroscopy. Schottky-barrier-height measurements on n-type Si (100) have also been performed in the temperature range of 95-295 K with the use of a current-voltage technique. The results show that a metal-rich compound with a composition in the Cu3Si range forms at low temperatures (473 K). The electronic properties of the compound are dominated by the hybridization between the Cu(d) and Si(p) valence states. A direct consequence of this hybridization is the peculiar oxidation behavior of the compound surface; both Cu and Si have been found to oxidize at room temperature. The oxidation of Si in the silicide is enhanced as compared with the oxidation of the elemental single-crystalline Si surface. Upon annealing the oxidized surface, a solid state reaction takes place: Cu2O disappears and a thicker SiO2 layer grows, owing to the large difference in free energies of formation between SiO2 and Cu2O. The n-type barrier height of 0.79 eV for both the as-deposited metal and the metal-rich silicide phase decreases with increasing temperature with a coefficient close to the temperature coefficient of the indirect energy gap in Si. These results suggest that the Fermi level at the interface is pinned relative to the valence-band edge, independent of temperature.

The common practice for nickel silicide formation in silicon nanowires (SiNWs) relies on axial growth of silicide along the wire that is initiated from nickel reservoirs at the source and drain contacts. In the present work the silicide intrusions were studied for various parameters including wire diameter (25-50 nm), annealing time (15-120 s), annealing temperature (300-440∘C), and the quality of the initial Ni/Si interface. The silicide formation was investigated by high-resolution scanning electron microscopy, high-resolution transmission electron microscopy (TEM), and atomic force microscopy. The main part of the intrusion formed at 420∘C consists of monosilicide NiSi, as was confirmed by energy dispersive spectroscopy STEM, selected area diffraction TEM, and electrical resistance measurements of fully silicided SiNWs. The kinetics of nickel silicide axial growth in the SiNWs was analyzed in the framework of a diffusion model through constrictions. The model calculates the time dependence of the intrusion length, L, and predicts crossover from linear to square root time dependency for different wire parameters, as confirmed by the experimental data.

The overall objective of this program is to develop structural silicide-based materials with optimum combinations of elevated temperature strength/creep resistance, low temperature fracture toughness, and high temperature oxidation and corrosion resistance for applications of importance to the US processing industry. A further objective is to develop silicide-based prototype industrial components. The ultimate aim of the program is to work with industry to transfer the structural silicide materials technology to the private sector in order to promote international competitiveness in the area of advanced high temperature materials and important applications in major energy-intensive US processing industries. The program presently has a number of developing industrial connections, including a CRADA with Johns Manville Corporation targeted at the area of MoSi{sub 2}-based high temperature materials and components for fiberglass melting and processing applications. The authors are also developing an interaction with the Institute of Gas Technology (IGT) to develop silicides for high temperature radiant gas burner applications, for the glass and other industries. With Combustion Technology Inc., they are developing silicide-based periscope sight tubes for the direct observation of glass melts. With Accutru International Corporation, they are developing silicide-based protective sheaths for self-verifying temperature sensors which may be used in glass furnaces and other industrial applications. The progress made on the program in this period is summarized.

Theoretical investigations of the electronic structure, synthesis, and all-optical magnetization switching of transition-metal silicide nanostructures are reported. The magnetic moment of the nanostructures is studied as a function of the silicide cluster size and configuration. The experimentally demonstrated magnetization switching of nanostructured nickel silicide by circularly polarized light makes it possible to create high-speed storage devices with high density data recording.

Using temperature controlled Si and C ion implantation, we studied the effects of pre-amorphization implantation on NiPt alloy silicide phase formation. In situ synchrotron x-ray diffraction and resistance measurements were used to monitor phase and morphology evolution in silicide films. Results show that substrate amorphization strongly modulate the nucleation of silicide phases, regardless of implant species. However, morphological stability of the thin films is mainly enhanced by C addition, independently of the amorphization depth.

Using temperature controlled Si and C ion implantation, we studied the effects of pre-amorphization implantation on NiPt alloy silicide phase formation. In situ synchrotron x-ray diffraction and resistance measurements were used to monitor phase and morphology evolution in silicide films. Results show that substrate amorphization strongly modulate the nucleation of silicide phases, regardless of implant species. However, morphological stability of the thin films is mainly enhanced by C addition, independently of the amorphization depth.

The Si/NiSi(,2)(111) interface is of both fundamental and techno- logical interest: From the fundamental point of view, it is the best characterized of all semiconductor/metal interfaces, with two well-determined geometries (A and B) involving nearly perfect bonding. (This is because Si and NiSi(,2) have nearly the same lattice spacing.) Consequently, a theoretical treatment of this system makes sense--as it would not for messier systems--and one can have some confidence that the theoretical predictions are relevant to experimental observa- tions. From the technological point of view, Si/NiSi(,2) is representative of the class of semiconductor/metal interfaces that are currently of greatest interest in regard to electronic devices--Si/transition -metal-silicide interfaces. The calculations of this dissertation are for the intrinsic interface states of Si/NiSi(,2)-A geometry. These calculations also provide a foundation for later studies of defects at this interface, and for studies of other related systems, such as CoSi(,2). The calculations employ empirical tight-binding Hamiltonians for both Si and NiSi(,2) (with the parameters fitted to prior calculations of the bulk band structures, which appear to be in agreement with the available experimental data on bulk Si and NiSi(,2)). They also employ Green's function techniques--in particular, the subspace Hamiltonian technique. Our principal results are the following: (1) Interface state disper- sion curves are predicted along the symmetry lines (')(GAMMA)(')M, (')M(')K and (')K(')(GAMMA) of the surface Brillouin zone. (2) A prominent band of interface states is found which disperses downward from an energy within the Si band gap to an energy below the Si valence band edge E(,(upsilon)) as the planar wavevector (')k increases from (')(GAMMA) ((')k = 0) to (')M or (')K (symmetry points at boundary of the surface Brillouin zone). This band of inter- face states should be observable. It produces a peak in the surface

Nanodisk-shaped, single-crystal gold silicide heterojunctions were inserted into silicon nanowires during vapor-liquid-solid growth using Au as a catalyst within a specific range of chlorine-to-hydrogen atomic ratio. The mechanism of nanodisk formation has been investigated by changing the source gas ratio of SiCl4 to H2. We report that an over-supply of silicon into the Au-Si liquid alloy leads to highly supersaturated solution and enhances the precipitation of Au in the silicon nanowires due to the formation of unstable phases within the liquid alloy. It is shown that the gold precipitates embedded in the silicon nanowires consisted of a metastable gold silicide. Interestingly, faceting of gold silicide was observed at the Au/Si interfaces, and silicon nanowires were epitaxially grown on the top of the nanodisk by vapor-liquid-solid growth. High resolution transmission electron microscopy confirmed that gold silicide nanodisks are epitaxially connected to the silicon nanowires in the direction of growth direction. These gold silicide nanodisks would be useful as nanosized electrical junctions for future applications in nanowire interconnections. PMID:22121669

Mass spectrometric and target collection experiments were made at 1600 K to elucidate the mode of oxidative vaporization of two columbium alloys, fused-slurry-coated with a complex silicide former (Si-20Cr-Fe). At oxygen pressures up to 0.0005 torr the major vapor component detected by mass spectrometry for oxidized samples was gaseous silicon monoxide. Analysis of condensates collected at oxygen pressures of 0.1, 1.0 and 10 torr revealed that chromium-, silicon-, iron- and tungsten- containing species were the major products of vaporization. Equilibrium thermochemical diagrams were constructed for the metal-oxygen system corresponding to each constituent metal in both the coating and base alloy. The major vaporizing species are expected to be the gaseous oxides of chromium, silicon, iron and tungsten. Plots of vapor phase composition and maximum vaporization rate versus oxygen pressure were calculated for each coating constituent. The major contribution to weight loss by vaporization at oxygen pressures above 1 torr was shown to be the chromium-containing species.

Large-area synthesis of high-quality graphene by chemical vapour deposition on metallic substrates requires polishing or substrate grain enlargement followed by a lengthy growth period. Here we demonstrate a novel substrate processing method for facile synthesis of mm-sized, single-crystal graphene by coating polycrystalline platinum foils with a silicon-containing film. The film reacts with platinum on heating, resulting in the formation of a liquid platinum silicide layer that screens the platinum lattice and fills topographic defects. This reduces the dependence on the surface properties of the catalytic substrate, improving the crystallinity, uniformity and size of graphene domains. At elevated temperatures growth rates of more than an order of magnitude higher (120 μm min−1) than typically reported are achieved, allowing savings in costs for consumable materials, energy and time. This generic technique paves the way for using a whole new range of eutectic substrates for the large-area synthesis of 2D materials. PMID:26175062

Manganese is one of the most important ferrous metals and one of the few for which the United States is totally dependent on imports. It is a black, brittle element predominantly used in metallurgical applications as an alloying addition, particularly in steel and cast iron production, which together provide the largest market for manganese (about 83 percent). It is also used as an alloy with nonferrous metals such as aluminum and copper. Nonmetallurgical applications of manganese include battery cathodes, soft ferrite magnets used in electronics, micronutrients found in fertilizers and animal feed, water treatment chemicals, and a colorant for bricks and ceramics.

Aiming to realize a conductive passivation layer for copper interconnection, the solid-gas reactions of cobalt films with silane and with disilane to form cobalt silicides are experimentally investigated. X-ray photoelectron spectroscopy revealed that cobalt silicides layers of up to 6 nm thickness can be selectively formed in the reaction at 473-673 K within 5 min without detectable silicon deposition on silicon dioxide, a common inter-metal dielectric layer. Rapid thermal oxidation experiments revealed that the silicided cobalt layers had better anti-oxidation performance than untreated cobalt layers, and the effect of silicidation was to suppress copper out-diffusion through the cobalt layers. Because cobalt-based alloys can be selectively electroless-plated on copper, selective silicidation of cobalt layers will be easily incorporated into device processing.

Copper-silicide precipitates in silicon obtained after copper diffusion and quench in different liquids were studied by transmission electron microscopy and capacitance spectroscopy techniques. A correlation between the quenching rate, geometric size, and deep level spectra of the copper-silicide precipitates was established. The unusually wide deep level spectra are shown to be due to a defect-related band in the bandgap. The parameters of the band are evaluated using numerical simulations. a positive charge of copper-silicide precipitates in p-type and moderately doped n-type Si is predicted by simulations and confirmed by minority carrier transient spectroscopy measurements. Strong recombination activity of the precipitates due to attraction of minority carriers by the electric field around the precipitates and their recombination via the defect band is predicted and confirmed by the experiments. The pairing of copper with boron is shown to be an important factor determining the precipitation kinetics of the interstitial copper at room temperature.

Iron silicide (cubic FeSi2) nanowires have been grown on Si(110) by reactive deposition epitaxy and investigated by scanning tunneling microscopy and scanning/transmission electron microscopy. On an otherwise uniform nanowire, a semi-periodic pattern along the edges of FeSi2 nanowires has been discovered. The origin of such growth patterns has been traced to initial growth of silicide nanodots with a pyramidal Si base at the chevron-like atomic arrangement of a clean reconstructed Si(110) surface. The pyramidal base evolves into a comb-like structure along the edges of the nanowires. This causes the semi-periodic structure of the iron silicide nanowires along their edges.

Nickel silicides have been grown on single crystal silicon sub- strates. A XeCl excimer laser was used for all process steps: substrate cleaning, nickel deposition , silicide formation and annealing. The nickel films were grown by photodecoxnposition of Ni(CO)4 adsorbate layers with an excess of CO to prevent homogeneous nucleation and hence the formation of dust. The samples were analysed by X-ray fluorescence, SIMS and RBS. The results indicate that epitaxial silicide layers with a thickness of 50 ma can be obtained after careful choice of laser fluence and Ni film thickness. In an alternative approach we used a molecular beam of Ni(CO)4, part of which is laser excited prior to impinging on the substrate. This allows the combination of CVD and conventional MBE techniques. In this experiment we also investigate the interaction of photofragments with substrate surfaces and other processes responsible for material deposition.

Silicon or germanium-based transistors are nowadays used in direct contact with silicide or germanide crystalline alloys for semiconductor device applications. Since these compounds are formed at elevated temperatures, accurate knowledge of the thermal expansion of both substrate and the contact is important to address temperature depending effects such as thermal stress. Here we report the linear coefficients of thermal expansion of Ni-, Pd- and Pt-based mono-germanides, mono-silicides and di-metal-silicides as determined by powder-based x-ray diffraction between 300 and 1225 K. The investigated mono-metallic compounds, all sharing the MnP crystal structure, as well as Pd2Si and Pt2Si exhibit anisotropic expansion. By consequence, this anisotropic behaviour should be taken into account for evaluating the crystal unit’s cell at elevated temperatures.

In the context of nickel silicide formation from plated nickel layers for solar cell metallization, there are several open questions regarding contact adhesion and electrical properties. Nanoscale characterization by transmission electron microscopy has been employed to support these investigations. Interfacial oxides and silicide phases were investigated on differently prepared samples by different analytical methods associated with transmission electron microscopy analysis. Processing variations included the pre-treatment of samples before nickel plating, the used plating solution and the thermal budget for the nickel-silicon solid-state reaction. It was shown that interface oxides of only few nm thickness on both silicon and nickel silicide are present on the samples, depending on the chosen process sequence, which have been shown to play an important role in adhesion of nickel on silicide in an earlier publication. From sample pretreatment variations, conclusions about the role of an interfacial oxide in silicide formation and its influence on phase formation were drawn. Such an oxide layer hinders silicide formation except for pinhole sites. This reduces the availability of Ni and causes a silicide with low Ni content to form. Without an interfacial oxide a continuous nickel silicide of greater depth, polycrystalline modification and expected phase according to thermal budget is formed. Information about the nature of silicide growth on typical solar cell surfaces could be obtained from silicide phase and geometric observations, which were supported by FIB tomography. The theory of isotropic NiSi growth and orientation dependent NiSi2 growth was derived. By this, a very well performing low-cost metallization for silicon solar cells has been brought an important step closer to industrial introduction.

The presence of manganese in natural waters (>0.05 mg/L) degrades water-supply quality. A model was devised to predict the variation of manganese concentrations in river water released from an impoundment with the distance downstream. The model is one-dimensional and was calibrated using dissolved oxygen, biochemical oxygen demand, pH, manganese, and hydraulic data collected in the Duck River, Tennessee. The results indicated that the model can predict manganese levels under various conditions. The model was then applied to the Chattahoochee River, Georgia. Discrepancies between observed and predicted may be due to inadequate pH data, precipitation of sediment particles, unsteady flow conditions in the Chattahoochee River, inaccurate rate expressions for the low pH conditions, or their combinations.

Thermoelectric devices directly convert heat into electricity and are very attractive for waste heat recovery and solar energy utilization. If thermoelectric devices can be made sufficiently efficient and inexpensive, then they will become a transformative energy technology that can tap a significant portion (10-20%) of the vast amount of heat existing in nature as well as industrial processes. Nanopowders of Earth-abundant, silicide-based materials, such as Mg2Si and its alloys, provide a unique opportunity to realize this goal. This article will present an overview of recent advances in the synthesis and thermoelectric properties of silicide-based nanostructured materials.

Metallic silicide films are formed on silicon substrates by contacting the substrates with a low-energy ion beam of metal ions while moderately heating the substrate. The heating of the substrate provides for the diffusion of silicon atoms through the film as it is being formed to the surface of the film for interaction with the metal ions as they contact the diffused silicon. The metallic silicide films provided by the present invention are contaminant free, of uniform stoichiometry, large grain size, and exhibit low resistivity values which are of particular usefulness for integrated circuit production.

A novel use of Ti marker is introduced to investigate the moving species during Pd2Si formation on 111 and 100 line-type Si substrates. Silicide formed from amorphous Si is also studied using a W marker. Although these markers are observed to alter the silicide formation in the initial stage, the moving species can be identified once a normal growth rate is resumed. It is found that Si is the dominant moving species for all three types of Si crystallinity. However, Pd will participate in mass transport when Si motion becomes obstructed.

This paper outlines the thermal analysis for the irradiation of high density uranium-silicide (U3Si2 dispersed in an aluminum matrix and clad in aluminum) booster fuel for a Boosted Fast Flux Loop designed to provide fast neutron flux test capability in the ATR. The purpose of this experiment (designated as Gas Test Loop-1 [GTL-1]) is two-fold: (1) to assess the adequacy of the U3Si2/Al dispersion fuel and the aluminum alloy 6061 cladding, and (2) to verify stability of the fuel cladding boehmite pre-treatment at nominal power levels in the 430 to 615 W/cm2 (2.63 to 3.76 Btu/s•in2) range. The GTL-1 experiment relies on a difficult balance between achieving a high heat flux, yet keeping fuel centerline temperature below a specified maximum value throughout an entire operating cycle of the reactor. A detailed finite element model was constructed to calculate temperatures and heat flux levels and to reveal which experiment parameters place constraints on reactor operations. Analyses were performed to determine the bounding lobe power level at which the experiment could be safely irradiated, yet still provide meaningful data under nominal operating conditions. Then, simulations were conducted for nominal and bounding lobe power levels under steady-state and transient conditions with the experiment in the reactor. Reactivity changes due to a loss of commercial power with pump coast-down to emergency flow or a standard in-pile tube pump discharge break were evaluated. The time after shutdown for which the experiment can be adequately cooled by natural convection cooling was determined using a system thermal hydraulic model. An analysis was performed to establish the required in-reactor cooling time prior to removal of the experiment from the reactor. The inclusion of machining tolerances in the numerical model has a large effect on heat transfer.

The bandgap and optical properties of diamond silicon (Si) are not suitable for many advanced applications such as thin-film photovoltaic devices and light-emitting diodes. Thus, finding new Si allotropes with better bandgap and optical properties is desirable. Recently, a Si allotrope with a desirable bandgap of ∼1.3 eV was obtained by leaching Na from NaSi6 that was synthesized under high pressure [Nat. Mater. 2015, 14, 169], paving the way to finding new Si allotropes. Li is isoelectronic with Na, with a smaller atomic core and comparable electronegativity. It is unknown whether Li silicides share similar properties, but it is of considerable interest. Here, a swarm intelligence-based structural prediction is used in combination with first-principles calculations to investigate the chemical reactions between Si and Li at high pressures, where seven new compositions (LiSi4, LiSi3, LiSi2, Li2Si3, Li2Si, Li3Si, and Li4Si) become stable above 8.4 GPa. The Si-Si bonding patterns in these compounds evolve with increasing Li content sequentially from frameworks to layers, linear chains, and eventually isolated Si ions. Nearest-neighbor Si atoms, in Cmmm-structured LiSi4, form covalent open channels hosting one-dimensional Li atom chains, which have similar structural features to NaSi6. The analysis of integrated crystal orbital Hamilton populations reveals that the Si-Si interactions are mainly responsible for the structural stability. Moreover, this structure is dynamically stable even at ambient pressure. Our results are also important for understanding the structures and electronic properties of Li-Si binary compounds at high pressures. PMID:27302244

Bog manganese ore, associated with the banded iron formation of the Iron Ore Group (IOG), occurs in large volume in northern Odisha, India. The ore is powdery, fine-grained and soft in nature with varying specific gravity (2.8-3.9 g/cm3) and high thermo-gravimetric loss, It consists of manganese (δ-MnO2, manganite, cryptomelane/romanechite with minor pyrolusite) and iron (goethite/limonite and hematite) minerals with sub-ordinate kaolinite and quartz. It shows oolitic/pisolitic to globular morphology nucleating small detritus of quartz, pyrolusite/romanechite and hematite. The ore contains around 23% Mn and 28% Fe with around 7% of combined alumina and silica. Such Mn ore has not found any use because of its sub-grade nature and high iron content, and is hence considered as waste. The ore does not respond to any physical beneficiation techniques because of the combined state of the manganese and iron phases. Attempts have been made to recover manganese and iron value from such ore through smelting. A sample along with an appropriate charge mix when processed through a plasma reactor, produced high-manganese steel alloy having 25% Mn within a very short time (<10 min). Minor Mn content from the slag was recovered through acid leaching. The aim of this study has been to recover a value-added product from the waste.

Extraction of manganese from electrolytic manganese residues using bioleaching was investigated in this paper. The maximum extraction efficiency of Mn was 93% by sulfur-oxidizing bacteria at 4.0 g/l sulfur after bioleaching of 9days, while the maximum extraction efficiency of Mn was 81% by pyrite-leaching bacteria at 4.0 g/l pyrite. The series bioleaching first by sulfur-oxidizing bacteria and followed by pyrite-leaching bacteria evidently promoted the extraction of manganese, witnessing the maximum extraction efficiency of 98.1%. In the case of sulfur-oxidizing bacteria, the strong dissolution of bio-generated sulfuric acid resulted in extraction of soluble Mn2+, while both the Fe2+ catalyzed reduction of Mn4+ and weak acidic dissolution of Mn2+ accounted for the extraction of manganese with pyrite-leaching bacteria. The chemical simulation of bioleaching process further confirmed that the acid dissolution of Mn2+ and Fe2+ catalyzed reduction of Mn4+ were the bioleaching mechanisms involved for Mn extraction from electrolytic manganese residues. PMID:21050747

Bog manganese ore, associated with the banded iron formation of the Iron Ore Group (IOG), occurs in large volume in northern Odisha, India. The ore is powdery, fine-grained and soft in nature with varying specific gravity (2.8-3.9 g/cm3) and high thermo-gravimetric loss, It consists of manganese (δ-MnO2, manganite, cryptomelane/romanechite with minor pyrolusite) and iron (goethite/limonite and hematite) minerals with sub-ordinate kaolinite and quartz. It shows oolitic/pisolitic to globular morphology nucleating small detritus of quartz, pyrolusite/romanechite and hematite. The ore contains around 23% Mn and 28% Fe with around 7% of combined alumina and silica. Such Mn ore has not found any use because of its sub-grade nature and high iron content, and is hence considered as waste. The ore does not respond to any physical beneficiation techniques because of the combined state of the manganese and iron phases. Attempts have been made to recover manganese and iron value from such ore through smelting. A sample along with an appropriate charge mix when processed through a plasma reactor, produced high-manganese steel alloy having 25% Mn within a very short time (<10 min). Minor Mn content from the slag was recovered through acid leaching. The aim of this study has been to recover a value-added product from the waste.

We report on formation of non-crystalline Fe-silicides of various stoichiometries below the amorphized surface of crystalline Si(001) after irradiation with 5 keV Fe{sup +} ions under off-normal incidence. We examined samples prepared with ion fluences of 0.1 × 10{sup 17} and 5 × 10{sup 17} ions cm{sup −2} exhibiting a flat and patterned surface morphology, respectively. Whereas the iron silicides are found across the whole surface of the flat sample, they are concentrated at the top of ridges at the rippled surface. A depth resolved analysis of the chemical states of Si and Fe atoms in the near surface region was performed by combining X-ray photoelectron spectroscopy and X-ray absorption spectroscopy (XAS) using synchrotron radiation. The chemical shift and the line shape of the Si 2p core levels and valence bands were measured and associated with the formation of silicide bonds of different stoichiometric composition changing from an Fe-rich silicides (Fe{sub 3}Si) close to the surface into a Si-rich silicide (FeSi{sub 2}) towards the inner interface to the Si(001) substrate. This finding is supported by XAS analysis at the Fe K-edge which shows changes of the chemical environment and the near order atomic coordination of the Fe atoms in the region close to surface. Because a similar Fe depth profile has been found for samples co-sputtered with Fe during Kr{sup +} ion irradiation, our results suggest the importance of chemically bonded Fe in the surface region for the process of ripple formation.

Carbon spheres have been prepared from glucose under hydrothermal conditions to facilitate the synthesis of hollow manganese oxides. The phases of manganese oxide are controlled by changing annealing temperature of the manganese monoxide on a carbon sphere template. The particles on the carbon surface get an agglomeration and make dense oxide shell during the calcination step, which result in typical hollow structures. The electrochemical properties of hollow manganese oxides have been investigated to elucidate their relative catalytic activities. PMID:27433689

It has previously been reported that moderately high dietary manganese (Mn) in combination with marginal magnesium (Mg) resulted in ultrastructural damage to heart mitochondria. Manganese may replace Mg in biological functions, including the role of enzyme cofactor. Manganese may accumulate and subs...

The preparation of U/sup 235/ and an improved method for isolating Pa/ sup 233/ from foreign products present in neutronirradiated thorium is described. The method comprises forming a solution of neutron-irradiated thorium together with a manganous salt, then adding potassium permanganate to precipitate the manganese as manganese dioxide whereby protoactinium is carried down with the nnanganese dioxide dissolving the precipitate, adding a soluble zirconium salt, and adding phosphate ion to precipitate zirconium phosphate whereby protoactinium is then carried down with the zirconium phosphate to effect a further concentration.

Single photon avalanche diode (SPAD) is an attractive solid-state optical detector that offers ultra-high photon sensitivity (down to the single photon level), high speed (sub-nanosecond dead time) and good timing performance (less than 100 ps). In this work, the impact of the silicide layer on SPAD’s characteristics, including the breakdown voltage, dark count rate (DCR), after-pulsing probability and photon detection efficiency (PDE) is investigated. For this purpose, two sets of SPAD structures in a standard 130 nm complementary metal oxide semiconductor (CMOS) process are designed, fabricated, measured and compared. A factor of 4.5 (minimum) in DCR reduction, and 5 in PDE improvements are observed when the silicide layer is removed from the SPAD structure. However, the after-pulsing probability of the SPAD without silicide layer is two times higher than its counterpart with silicide. The reasons for these changes will be discussed.

The experimental and coating process details are presented. The process specifications which were developed for the formulation and application of the R-512E fused slurry silicide coating using either an acrylic or nitrocellulose base slurry system is also discussed.

Nickel silicide nanowire arrays have been achieved by the decomposition of SiH(4) on Ni foil at 650 °C. It is indicated that the nickel silicide nanowires consist of roots with diameter of about 100-200 nm and tips with diameter of about 10-50 nm. A Ni diffusion controlled mechanism is proposed to explain the formation of the nickel silicide nanowires. Field emission measurement shows that the turn-on field of the nickel silicide nanowire arrays is low, at about 3.7 V µm(-1), and the field enhancement factor is as high as 4280, so the arrays have promising applications as emitters. PMID:21832554

The surface chemistry of dimanganese decacarbonyl on the native oxide of Si(100) wafers was characterized with the aid of x-ray photoelectron spectroscopy. Initial experiments in a small stainless-steel reactor identified a narrow range of temperatures, between approximately 445 and 465 K, in which the deposition of manganese could be achieved in a self-limiting fashion, as is desirable for atomic layer deposition. Deposition at higher temperatures leads to multilayer growth, but the extent of this Mn deposition reverses at even higher temperatures (about 625 K), and also ifhydrogen is added to the reaction mixture. Extensive decarbonylation takes place below room temperature, but limited C-O bond dissociation and carbon deposition are still seen after high exposures at 625 K. The films deposited at low ({approx}450 K) temperatures are mostly in the form of MnO, but at 625 K that converts to a manganese silicate, and upon higher doses a manganesesilicide forms at the SiO{sub 2}/Si(100) interface as well. No metallic manganese could be deposited with this precursor on either silicon dioxide or copper surfaces.

With a view to explore the influence of essential metals in manganese intoxication, the effect of calcium, iron or zinc supplementation on the uptake of manganese and on the activity of manganese sensitive enzymes, succinic dehydrogenase and cytochrome oxidase in brain and liver of rat was investigated. The choice of the two mitochondrial enzymes was based on the fact that the mitochondria are the chief site of manganese accumulation and their activity in brain, liver and blood of rats is significantly influenced by manganese.

We show that surface arc-discharge deposited carbon plays a critical intermediary role in the breakdown of thermally grown oxide diffusion barriers of 90 nm on a silicon wafer at 1035 °C in an Ar/H{sub 2} atmosphere, resulting in the formation of epitaxial copper silicide particles in ≈ 10 μm wide channels, which are aligned with the intersections of the (100) surface of the wafer and the (110) planes on an oxidized silicon wafer, as well as endotaxial copper silicide nanoparticles within the wafer bulk. We apply energy dispersive x-ray spectroscopy, in combination with scanning and transmission electron microscopy of focused ion beam fabricated lammelas and trenches in the structure to elucidate the process of their formation.

Results are reported of a research program to develop a reliable high-performance, fused slurry silicide protective coating for a tantalum-10 tungsten alloy for use at 1427 to 1538 C at 0.1 to 10 torr air pressure under cyclic temperature conditions. A review of silicide coating performance under these conditions indicated that the primary wear-out mode is associated with widening of hairline fissures in the coating. Consideration has been given to modifying the oxidation products that form on the coating surface to provide a seal for these fissures and to minimize their widening. On the basis of an analysis of the phase relationships between silica and various other oxides, a coating having the slurry composition 2.5Mn-33Ti-64.5Si was developed that is effective in the pressure range from 1 to 10 torr.

Aligned carbon nanotubes have been grown using microwave plasma enhanced chemical vapor deposition (PECVD). The carbon nanotubes are nucleated from iron catalyst particles which, during growth, remain adherent to the silicon substrates. By analysis with high-resolution electron microscopy, we observe iron silicide roots penetrating into the silicon substrate at the interface of the catalyst particles and the substrate, thus providing strong adhesion of the carbon nanotubes onto the substrate. The iron silicide roots assist in the attachment of the catalyst particles to the substrate and play a role in the evolution of the catalyst particle morphology and resulting base growth mode. Carbon nanotubes grown by microwave PECVD could exhibit superior electrical and thermal transport properties over other PECVD processes, so an understanding of the growth mechanism is important for utilization in device applications. PMID:16375415

The formation of Fe silicides in surface ripple patterns, generated by erosion of a Si surface with keV Ar and Xe ions and simultaneous co-deposition of Fe, was investigated with conversion electron Mössbauer spectroscopy, atomic force microscopy and Rutherford backscattering spectrometry. For the dot and ripple patterns studied, we find an average Fe concentration in the irradiated layer between 6 and 25 at.%. The Mössbauer spectra clearly show evidence of the formation of Fe disilicides with Fe content close to 33 at.%, but very little evidence of the formation of metallic Fe particles. The results support the process of ion-induced phase separation toward an amorphous Fe disilicide phase as pattern generation mechanism. The observed amorphous phase is in agreement with thermodynamic calculations of amorphous Fe silicides.

In this work, cobalt silicide nanowires were synthesized by chemical vapor deposition processes on Si (100) substrates with anhydrous cobalt chloride (CoCl2) as precursors. Processing parameters, including the temperature of Si (100) substrates, the gas flow rate, and the pressure of reactions were varied and studied; additionally, the physical properties of the cobalt silicide nanowires were measured. It was found that single-crystal CoSi nanowires were grown at 850°C ~ 880°C and at a lower gas flow rate, while single-crystal Co2Si nanowires were grown at 880°C ~ 900°C. The crystal structure and growth direction were identified, and the growth mechanism was proposed as well. This study with field emission measurements demonstrates that CoSi nanowires are attractive choices for future applications in field emitters. PMID:23819795

We have used medium-energy ion scattering (MEIS) to quantitatively analyze the structure of holmium silicide islands grown on the Si(100) surface. Structure fitting to the experimental data unambiguously shows that the tetragonal silicide phase is present and not the hexagonal phase, which is associated with the growth of nanowires at submonolayer coverages. Islands formed with a lower holmium coverage of 3 ML are also shown to be tetragonal, which suggests that the hexagonal structure is not a low coverage precursor to the growth of the tetragonal phase. MEIS simulations of large nanoislands, which include the effects of lateral strain relief, have been performed and these compare well with the experimental data.

The irradiation behavior of high-density uranium silicides has been a matter of interest to the nuclear industry for use in high power or low enrichment applications. Transmission electron microscopy studies have found that heavy ion bombardment renders U{sub 3}Si and U{sub 3}Si{sub 2} amorphous at temperatures below about 250 C and that U{sub 3}Si becomes mechanically unstable suffering rapid growth by plastic flow. In this present work, crystallographic changes preceding amorphization by fission fragment damage have been studied by high-resolution neutron diffraction as a function of damage produced by uranium fission at room temperature. Initially, both silicides had tetragonal crystal structures. Crystallographic and amorphous phases were studied simultaneously by combining conventional Rietveld refinement of the crystallographic phases with Fourier-filtering analysis of the non-crystalline scattering component. 13 refs., 5 figs.

Manganese oxide nanoparticles were prepared by thermal decomposition of manganese oxalate. Manganese oxalate was synthesized by reacting 1:1 mole ratio of manganese acetate and ammonium oxalate along with sodium dodecyl sulfate (SDS). The structural characterization of manganese oxalate and manganese oxide nanoparticles was analyzed by XRD. The XRD spectrum confirms the crystal structure of the manganese oxide and manganese oxalate. In addition, the average grain size, lattice parameter values were also calculated using XRD spectrum. Moreover, the diffraction peaks were broadened due to the smaller size of the particle. The band gap of manganese oxide was calculated from optical absorption, which was carried out by DRS UV-Visible spectroscopy. The morphology of manganese oxide nanoparticles was analyzed by SEM images. The FT-IR analysis confirms the formation of the manganese oxide from manganese oxalate nanoparticles. The electrochemical sensing behavior of manganese oxide nanoparticles were investigated using hydrogen peroxide by cyclic voltammetry.

A combined silicide coating, including inner NbSi2 layer and outer MoSi2 layer, was fabricated through a two-step method. The NbSi2 was deposited on niobium alloy by halide activated pack cementation (HAPC) in the first step. Then, supersonic atmospheric plasma spray (SAPS) was applied to obtain the outer MoSi2 layer, forming a combined silicide coating. Results show that the combined coating possessed a compact structure. The phase constitution of the combined coating prepared by HAPC and SAPS was NbSi2 and MoSi2, respectively. The adhesion strength of the combined coating increased nearly two times than that for single sprayed coating, attributing to the rougher surface of the HAPC-bond layer whose roughness increased about three times than that of the grit-blast substrate. After exposure at 1200 °C in air, the mass increasing rate for single HAPC-silicide coating was 3.5 mg/cm(2) because of the pest oxidation of niobium alloy, whereas the combined coating displayed better oxidation resistance with a mass gain of only 1.2 mg/cm(2). Even more, the combined coating could significantly improve the antioxidation ability of niobium based alloy at 1500 °C. The good oxidation resistance of the combined silicide coating was attributed to the integrity of the combined coating and the continuous SiO2 protective scale provided by the oxidation of MoSi2. PMID:27243944

Study of short-time high-temperature diffusion treatments as part of a program of development of methods of reapplying fused slurry silicide coating in the field. The metallographic structure and oxidation behavior of R512E applied to Cb-752 coated under simulated field repair conditions was determined. Oxidation testing in reduced pressure environment has shown that performance equivalent to furnace-processed specimens can be obtained in a two-minute diffusion at 2700 F.

This paper marks the initial study into the technical and economic feasibility of converting the SAFARI-1 reactor in South Africa to LEU silicide fuel. Several MTR assembly geometries and LEU uranium densities have been studied and compared with MEU and HEU fuels. Two factors of primary importance for conversion of SAFARI-1 to LEU fuel are the economy of the fuel cycle and the performance of the incore and excore irradiation positions.

The effect of impurities on the growth of the Pd2Si layer upon thermal annealing of a Pd film on 100 line-type and amorphous Si substrates is investigated. Nitrogen and oxygen impurities are introduced into either Pd or Si which are subsequently annealed to form Pd2Si. The complementary techniques of Rutherford backscattering spectrometry, and N-15(p, alpha)C-12 or O-18(p, alpha)N-15 nuclear reaction, are used to investigate the behavior of nitrogen or oxygen and the alterations each creates during silicide formation. Both nitrogen and oxygen retard the silicide growth rate if initially present in Si. When they are initially in Pd, there is no significant retardation; instead, an interesting snow-plowing effect of N or O by the reaction interface of Pd2Si is observed. By using N implanted into Si as a marker, Pd and Si appear to trade roles as the moving species when the silicide front reaches the nitrogen-rich region.

Platinum silicide Schottky diodes formed on films of polycrystalline Si doped by phosphorus are demonstrated to be efficient and manufacturable CMOS-compatible temperature sensors for microbolometer detectors of radiation. Thin-film platinum silicide/poly-Si diodes have been produced by a CMOS-compatible process on artificial Si{sub 3}N{sub 4}/SiO{sub 2}/Si(001) substrates simulating the bolometer cells. Layer structure and phase composition of the original Pt/poly-Si films and the Pt silicide/poly-Si films synthesized by a low-temperature process have been studied by means of the scanning transmission electron microscopy; they have also been explored by means of the two-wavelength X-ray structural phase analysis and the X-ray photoelectron spectroscopy. Temperature coefficient of voltage for the forward current of a single diode is shown to reach the value of about −2%/ °C in the temperature interval from 25 to 50 °C.

Platinum silicide Schottky diodes formed on films of polycrystalline Si doped by phosphorus are demonstrated to be efficient and manufacturable CMOS-compatible temperature sensors for microbolometer detectors of radiation. Thin-film platinum silicide/poly-Si diodes have been produced by a CMOS-compatible process on artificial Si3N4/SiO2/Si(001) substrates simulating the bolometer cells. Layer structure and phase composition of the original Pt/poly-Si films and the Pt silicide/poly-Si films synthesized by a low-temperature process have been studied by means of the scanning transmission electron microscopy; they have also been explored by means of the two-wavelength X-ray structural phase analysis and the X-ray photoelectron spectroscopy. Temperature coefficient of voltage for the forward current of a single diode is shown to reach the value of about -2%/ °C in the temperature interval from 25 to 50 °C.

Nickel silicide is one of the electrical contact materials widely used on very large scale integration (VLSI) of Si devices in microelectronic industry. This is because the silicide/silicon interface can be formed in a highly controlled manner to ensure reproducibility of optimal structural and electrical properties of the metal-Si contacts. These advantages can be inherited to Si nanowire (NW) field-effect transistors (FET) device. Due to the technological importance of nickel silicides, fundamental materials science of nickel silicides formation (Ni-Si reaction), especially in nanoscale, has raised wide interest and stimulate new insights and understandings. In this dissertation, in-situ transmission electron microscopy (TEM) in combination with FET device characterization will be demonstrated as useful tools in nano-device fabrication as well as in gaining insights into the process of nickel silicide formation. The shortest transistor channel length (17 nm) fabricated on a vapor-liquid-solid (VLS) grown silicon nanowire (NW) has been demonstrated by controlled reaction with Ni leads on an in-situ transmission electron microscope (TEM) heating stage at a moderate temperature of 400 ºC. NiSi2 is the leading phase, and the silicide-silicon interface is an atomically sharp type-A interface. At such channel lengths, high maximum on-currents of 890 (microA/microm) and a maximum transconductance of 430 (microS/microm) were obtained, which pushes forward the performance of bottom-up Si NW Schottky barrier field-effect transistors (SB-FETs). Through accurate control over the silicidation reaction, we provide a systematic study of channel length dependent carrier transport in a large number of SB-FETs with channel lengths in the range of (17 nm -- 3.6 microm). Our device results corroborate with our transport simulations and reveal a characteristic type of short channel effects in SB-FETs, both in on- and off-state, which is different from that in conventional MOSFETs

Thermoelectric modules consisting of n-type Mn2.7Cr0.3Si4Al2 and p-type MnSi1.75 legs have been fabricated by use of composite pastes of Ag with Pt or Pd. For the module prepared by Ni-B plating and with Ag paste, the specific power density reached 370 mW/cm2 at a heat-source temperature of 873 K. Ni-B plating 5 μm thick on the surfaces of the silicide legs reduced both the internal resistance and degradation of the power generated by silicide modules at temperatures up to 873 K in air. This is because of oxidation of Al diffusing into the n-type legs and reaching the Ag electrodes on both the hot and cold sides. Ni-B plating can suppress Al diffusion into n-type legs. However, cracking was observed parallel to the contact surface in the middle of the Ni-B plating layer on the p-type legs. It was also found that incorporating Pt or Pd into the Ag paste effectively suppressed degradation of the contact resistance between the silicide legs and the Ag electrodes.

Biological catalysis of manganese oxidation represents an important contribution to global manganese cycling; biological oxidation rates are several orders of magnitude higher than those of abiotic processes. Despite recent genetics advances, ongoing behavioral studies, and a large pool of knowledge regarding manganese chemistry, the links between biology and environmental chemistry remain unresolved. We have performed experiments on batch cultures of Leptothrix discophora SS-1 to explore the physiology of biological manganese oxidation. We have further conducted spectroscopic and microscopic studies of the mechanism as manganese proceeds from the soluble Mn2+ species to the insoluble Mn(III) and Mn(IV) phases. These investigations suggest roles for aqueous chemistry, mineralogy, and microbial physiology in controlling manganese fluxes in metal-rich environments.

Classic symptoms of manganese intoxication are very rarely seen nowadays. Clinic in Angarsk Research Institute for Occupational medicine and Human ecology registered two cases of stage I and II chronic manganese intoxication over 10 years among electric welders. The cases were diagnosed with consideration of long length of exposure to manganese with the ambient air level exceeding the MAC 1.5 times, the disease manifestation at middle age, high manganese level in serum and urine, characteristic neurologic symptoms in association with organic psychopathologic defects and polyneuropathy of limbs. PMID:19278189

Anthropogenic accumulation of metals such as manganese is a well-established health risk factor for vertebrates. By contrast, the long-term impact of these contaminants on invertebrates is mostly unknown. Here, we demonstrate that manganese ingestion alters brain biogenic amine levels in honeybees and fruit flies. Furthermore, we show that manganese exposure negatively affects foraging behaviour in the honeybee, an economically important pollinator. Our findings indicate that in addition to its direct impact on human health, the common industrial contaminant manganese might also have indirect environmental and economical impacts via the modulation of neuronal and behavioural functions in economically important insects. PMID:25808001

This letter reports on a process scheme to obtain highly reproducible Ni{sub 1-x}Pt{sub x} silicide films of 3-6 nm thickness formed on a Si(100) substrate. Such ultrathin silicide films are readily attained by sputter deposition of metal films, metal stripping in wet chemicals, and final silicidation by rapid thermal processing. This process sequence warrants an invariant amount of metal intermixed with Si in the substrate surface region independent of the initial metal thickness, thereby leading to a self-limiting formation of ultrathin silicide films. The crystallographic structure, thickness, uniformity, and morphological stability of the final silicide films depend sensitively on the initial Pt fraction.

The cellular accumulation and uptake kinetics of manganese by Chlamydomonas sp. were studied in model chelate buffer systems. Cellular manganese concentrations and uptake rates were related to the computed free manganese ion concentration and were independent of the total or chelated manganese concentration. Cellular manganese was constant at about 1 mmol liter/sup -1/ of cellular volume at free manganese ion concentrations of 10/sup -7/ /sup 6/-10/sup -6/ /sup 3/ mol liter/sup -1/ and decreased below this range. Manganese uptake rates followed saturation kinetics and V/sub max/, but not K/sub s/, varied with the free manganese ion concentration in the growth medium. V/sub max/ appeared to be under negative feedback control and increased with decreasing manganese ion concentration. Variations of up to 30-fold in this parameter seemed to be instrumental in limiting the variation in cellular manganese to a sixfold range despite a 1000-fold variation in free manganese ion concentration in the growth medium.

Atomic-resolution high-angle annular dark-field scanning-transmission electron microscopy and ab-initio calculations were used to reveal the reaction involved in the formation of ultra-thin Ni silicide film at 300°C. We found that a Ni-adamantane structure, in which Ni atoms occupy the tetrahedral interstitial voids of Si, forms at the initial stage of the reaction. We also found that the adamantane structure is under considerable compressive stress due to lattice-mismatch at the adamantane structure-Si interface (5.6%). Then, NiSi2 forms just beneath the Ni-adamantane structure at a much lower temperature than the NiSi2 formation temperature reported for the reaction between a Ni layer and Si substrate (800°C). Our analyses strongly suggest that the Ni-adamantane structure acts as a precursor in the formation of NiSi2.

Alloy films of NiPt were e-beam codeposited on n-type Si and annealed up to 700 °C in a purified- He ambient furnace. Silicide formation was monitored using MeV4 He Rutherford backscattering and glancing-angle x-ray diffraction. At low temperatures (300-350 °C), Ni segregates at the Si/ silicide interface and the first phases detected are NiSi and PtSi. At intermediate temperatures (400- 500 °C), there is further accumulation of Ni at the Si/silicide interface, and at later stages an incursion of Pt to the interface. The barrier height increase reflects the presence of Pt. At 700 °C, the Ni and Pt redistribute to form a uniform ternary.

The Th(230): Pa(231) activity ratio in 7 of 11 manganese nodules is less than 10.8, the theoretical production ratio of activities in the ocean. This finding indicates difierential accumulation of these nuclides in authigenic deposits of manganese-iron oxide. PMID:17778807

... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2775 Manganese violet. (a) Identity. The color additive... less than 93 percent. (c) Uses and restrictions. Manganese violet is safe for use in coloring cosmetics generally, including cosmetics applied to the area of the eye, in amounts consistent with good...

... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2775 Manganese violet. (a) Identity. The color additive... less than 93 percent. (c) Uses and restrictions. Manganese violet is safe for use in coloring cosmetics generally, including cosmetics applied to the area of the eye, in amounts consistent with good...

... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2775 Manganese violet. (a) Identity. The color additive... less than 93 percent. (c) Uses and restrictions. Manganese violet is safe for use in coloring cosmetics generally, including cosmetics applied to the area of the eye, in amounts consistent with good...

Until recently, quantitative EPMA of phases under a few microns in size has been extremely difficult. In order to achieve analytical volumes to analyze sub-micron features, accelerating voltages between 5 and 8 keV need to be used. At these voltages the normally used K X-ray transitions (of higher Z elements) are no longer excited, and we must rely of outer shell transitions (L and M). These outer shell transitions are difficult to use for quantitative EPMA because they are strongly affected by different bonding environments, the error associated with their mass attenuation coefficients (MAC), and their proximity to absorption edges. These problems are especially prevalent for the transition metals, because of the unfilled M5 electron shell where the Lα transition originates. Previous studies have tried to overcome these limitations by using standards that almost exactly matched their unknowns. This, however, is cumbersome and requires accurate knowledge of the composition of your sample beforehand, as well as an exorbitant number of well characterized standards. Using a 5 keV electron beam and utilizing non-standard X-ray transitions (Ll) for the transition metals, we are able to conduct accurate quantitative analyses of phases down to ~300nm. The Ll transition in the transition metals behaves more like a core-state transition, and unlike the Lα/β lines, is unaffected by bonding effects and does not lie near an absorption edge. This allows for quantitative analysis using standards do not have to exactly match the unknown. In our case pure metal standards were used for all elements except phosphorus. We present here data on iron-silicides in two Apollo 16 regolith grains. These plagioclase grains (A6-7 and A6-8) were collected between North and South Ray Craters, in the lunar highlands, and thus are associated with one or more large impact events. We report the presence of carbon, nickel, and phosphorus (in order of abundance) in these iron-silicide phases

The expression of manganese peroxidase in nitrogen-limited cultures of Phanerochaete chrysosporium is dependent on Mn, and initial work suggested that Mn regulates transcription of the mnp gene. In this study, using Northern (RNA) blot analysis of kinetic, dose-response, and inhibitor experiments, the authors demonstrate unequivocally that Mn regulates mnp gene transcription. The amount of mnp mRNA in cells of 4-day-old nitrogen-limited cultures is a direct function of the concentration of Mn in the culture medium up to a maximum of 180 {mu}M. Addition of Mn to nitrogen-limited Mn-deficient secondary metabolic (4-, 5-, and 6-day-old) cultures results in the appearance of mnp mRNA within 40 min. The appearance of this message is completely inhibited by the RNA synthesis inhibitor dactinomycin but not by the protein synthesis inhibitor cycloheximide. Furthermore, the amount of mnp mRNA produced is a direct function of the concentration of added Mn. In contrast, addition of Mn to low-nitrogen Mn-deficient 2- or 3-day-old cultures does not result in the appearance of mnp mRNA. Manganese peroxidase protein is detected by specific immunoprecipitation of the in vitro translation products of poly(A) RNA isolated from Mn-supplemented (but nor from Mn-deficient) cells. All of these results demonstrate that Mn, the substrate for the enzyme, regulates mnp gene transcription via a growth-stage-specific and concentration-dependent mechanism.

Molybdenum silicides and borosilicides are promising structural materials for gas-turbine power plants. A major challenge, however, is to simultaneously achieve high oxidation resistance and acceptable mechanical properties at high temperatures. For example, molybdenum disilicide (MoSi2) has excellent oxidation resistance and poor mechanical properties, while Mo-rich silicides such as Mo5Si3 (called T 1) have much better mechanical properties but poor oxidation resistance. One approach is based on the fabrication of MoSi2-T 1 composites that combine high oxidation resistance of MoSi2 and good mechanical properties of T1. Another approach involves the addition of boron to Mo-rich silicides for improving their oxidation resistance through the formation of a borosilicate surface layer. In particular, Mo 5SiB2 (called T2) phase is considered as an attractive material. In the thesis, MoSi2-T1 composites and materials based on T2 phase are obtained by mechanically activated SHS. Use of SHS compaction (quasi-isostatic pressing) significantly improves oxidation resistance of the obtained MoSi2-T1 composites. Combustion of Mo-Si-B mixtures for the formation of T2 phase becomes possible if the composition is designed for the addition of more exothermic reactions leading to the formation of molybdenum boride. These mixtures exhibit spin combustion, the characteristics of which are in good agreement with the spin combustion theory. Oxidation resistance of the obtained Mo-Si-B materials is independent on the concentration of Mo phase in the products so that the materials with a higher Mo content are preferable because of better mechanical properties. Also, T2 phase has been obtained by the chemical oven combustion synthesis technique.

Continuous very thin (2.5-3.0 nm) and thin (16-18 nm) ytterbium suicide films with some pinhole density (3×107- 1×108 cm-2) have been formed on Si(111) by solid phase epitaxy (SPE) and reactive deposition epitaxy (RDE) growth methods on templates. The stoichiometric ytterbium suicide (YbSi2) formation has shown in SPE grown films by AES and EELS data. Very thin Yb suicide films grown by RDE method had the silicon enrichment in YbSi2 suicide composition. The analysis of LEED data and AFM imaging has shown that ytterbium suicide films had non-oriented blocks with the polycrystalline structure. The analysis of scanning region length dependencies of the root mean square roughness deviation (σR(L)) for grown suicide films has shown that the formation of ytterbium suicide in SPE and RDE growth methods is determined by the surface diffusion of Yb atoms during the three-dimensional growth process. Optical functions (n, k, α, ɛ1, ɛ2, Im ɛ1-1, neff, ɛeff) of ytterbium silicide films grown on Si(1 1 1) have been calculated from transmittance and reflectance spectra in the energy range of 0.1-6.2 eV. Two nearly discrete absorption bands have been observed in the electronic structure of Yb silicide films with different composition, which connected with interband transitions on divalent and trivalent Yb states. It was established that the reflection coefficient minimum in R-spectra at energies higher 4.2 eV corresponds to the state density minimum in Yb suicide between divalent and trivalent Yb states. It was shown from optical data that Yb silicide films have the semi-metallic properties with low state densities at energies less 0.4 eV and high state densities at 0.5-2.5 eV.

Titanium silicide has the lowest resistivity of all the refractory metal silicides and has good thermal stability as well as excellent compatibility with Al metallization. It is used as an intermediate buffer layer between W vias and the Si substrate to provide good electrical contact in ULSI technology, whose submicron patterned features form the basis of the integrated circuits of today and tomorrow, in the self aligned silicide (salicide) formation process. TiSi{sub 2} exists in two phases: a metastable C49 base-centered orthorhombic phase with specific resistivity of 60-90 {mu}{Omega}-cm that is formed at a lower temperature (formation anneal) and the stable 12-15 {mu}{Omega}-cm resistivity face-centered orthorhombic C54 phase into which C49 is transformed with a higher temperature (conversion anneal) step. C54 is clearly the target for low resistivity VLSI interconnects. However, it has been observed that when dimensions shrink below 1/mic (or when the Ti thickness drops below several hundred angstroms), the transformation of C49 into C54 is inhibited and agglomeration often occurs in fine lines at high temperatures. This results in a rise in resistivity due to incomplete transformation to C54 and because of discontinuities in the interconnect line resulting from agglomeration. Spectromicroscopy is an appropriate tool to study the evolution of the TiSi2 formation process because of its high resolution chemical imaging ability which can detect bonding changes even in the absence of changes in the relative amounts of species and because of the capability of studying thick {open_quotes}as is{close_quotes} industrial samples.

Iron and manganese are natural constituents of the earth's crust and both elements create serious aesthetic problems in drinking water supplies. The occurrence of iron and manganese in groundwater, and problems arising from their presence, are reviewed. Four commonly used methods for iron and manganese removal are direct oxidation, addition of oxidation agents, ion exchange, and stabilization. These methods are discussed, as well as factors affecting iron and manganese removal, such as temperature, pH, dissolved oxygen, alkalinity, and other ions present. The above factors affect the removal methods differently and for these reasons, laboratory testing and studies should be made to evaluate the treatability of a water supply for iron and manganese removal.

Recently, we have demonstrated Ni silicide/poly-Si diodes as a budget alternative to SOI-diode temperature sensors in uncooled microbolometer FPAs. This paper introduces a solution still more suitable for industry: We have developed PtSi/poly-Si Schottky diodes for microbolometers. Ease of integration of the PtSi/poly-Si diode formation process into the CMOS technology, in analogy with the internal photoemission PtSi/Si IR FPAs, is the merit of the PtSi/poly-Si sensors. Now we demonstrate PtSi/poly-Si diode microbolometers and propose them as a promising solution for focal plane arrays.

Optical response to radiation at a wavelength of 10.6 microns in tungsten silicide-silicon Schottky barrier diodes has been observed. Incident photons excite electrons by means of junction plasmon assisted inelastic electron tunneling. At 78 K, a peak in the second derivative of current versus junction bias voltage was observed at a voltage corresponding to the energy of photons having a wavelength of 10.6 microns. This peak increased with increasing incident laser power, saturating at the highest laser powers investigated.

Alloys of transition metal suicides that contain one or more alloying elements are fabricated by a two-stage process involving mechanical activation as the first stage and densification and field-activated reaction as the second stage. Mechanical activation, preferably performed by high-energy planetary milling, results in the incorporation of atoms of the alloying element(s) into the crystal lattice of the transition metal, while the densification and field-activated reaction, preferably performed by spark plasma sintering, result in the formation of the alloyed transition metal silicide. Among the many advantages of the process are its ability to accommodate materials that are incompatible in other alloying methods.

Cells of Leptothrix discophora SS1 released Mn2+-oxidizing factors into the medium during growth in batch culture. Manganese was optimally oxidized when the medium was buffered with HEPES (N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid) at pH 7.5. Manganese-oxidizing activity in the culture medium in which this strain had been grown previously was sensitive to heat, phosphate, Tris, NaN3, HgCl2 NaCl, sodium dodecyl sulfate, and pronase; 0.5 mol of O2 was consumed per mol of MnO2 formed. During Mn2+ oxidation, protons were liberated. With sodium dodecyl sulfate-polyacrylamide gel electrophoresis, two protein-containing bands were detected in the spent culture medium. One band had an apparent molecular weight of 110,000 and was predominant in Mn2+-oxidizing activity. The second product (Mr 85,000) was only detected in some cases and probably represents a proteolytic breakdown moiety of the 110,000-Mr protein. The Mn2+-oxidizing factors were associated with the MnO2 aggregates that had been formed in spent culture medium. After solubilization of this MnO2 with ascorbate, Mn2+-oxidizing activity could be recovered. PMID:3804969

To reclaim treated steel wastewater as cooling water, manganese ore constructed wetland was proposed in this study for the removal of iron and manganese. In lab-scale wetlands, the performance of manganese ore wetland was found to be more stable and excellent than that of conventional gravel constructed wetland. The iron and manganese concentration in the former was below 0.05 mg/L at hydraulic retention time of 2-5 days when their influent concentrations were in the range of 0.16-2.24 mg/L and 0.11-2.23 mg/L, respectively. Moreover, its removals for COD, turbidity, ammonia nitrogen and total phosphorus were 55%, 90%, 67% and 93%, respectively, superior to the corresponding removals in the gravel wetland (31%, 86%, 58% and 78%, respectively). The good performance of manganese ore was ascribed to the enhanced biological manganese removal with the aid of manganese oxide surface and the smaller size of the medium. The presence of biological manganese oxidation was proven by the facts of good manganese removal in wetlands at chemical unfavorable conditions (such as ORP and pH) and the isolation of manganese oxidizing strains from the wetlands. Similar iron and manganese removal was later observed in a pilot-scale gravel-manganese-ore constructed wetland, even though the manganese ore portion in total volume was reduced from 100% (in the lab-scale) to only 4% (in the pilot-scale) for the sake of cost-saving. The quality of the polished wastewater not only satisfied the requirement for cooling water but also suitable as make-up water for other purposes. PMID:19443107

In collaboration with industry, Idaho National Laboratory is investigating uranium silicide for use in future light water reactor fuels as a more accident resistant alternative to uranium oxide base fuels. Specifically this project was focused on producing uranium silicide (U3Si2) pellets by conventional powder metallurgy with a density greater than 94% of the theoretical density. This work has produced a process to consistently produce pellets with the desired density through careful optimization of the process. Milling of the U3Si2 has been optimized and high phase purity U3Si2 has been successfully produced. Results are presented from sintering studies and microstructural examinationsmore » that illustrate the need for a finely ground reproducible particle size distribution in the source powder. The optimized process was used to produce pellets for the Accident Tolerant Fuel-1 irradiation experiment. The average density of these pellets was 11.54 ±0.06 g/cm3. Additional characterization of the pellets by scaning electron microscopy and X-ray diffraction has also been performed. As a result, pellets produced in this work have been encapsulated for irradiation, and irradiation in the Advanced Test Reactor is expected soon.« less

A single crystal of the title compound, the ternary silicide digadolinium trirhenium penta­silicide, Gd2Re3Si5, was isolated from an alloy of nominal composition Gd20Re30Si50 synthesized by arc melting and investigated by X-ray single-crystal diffraction. Its crystal structure belongs to the U2Mn3Si5 structure type. All atoms in the asymmetric lie on special positions. The Gd site has site symmetry m..; the two Mn atoms have site symmetries m.. and 2.22; the three Si atoms have site symmetries m.., ..2 and 4.. . The coordination polyhedra of the Gd atoms have 21 vertices, while those of the Re atoms are cubo­octa­hedra and 13-vertex polyhedra. The Si atoms are arranged as tricapped trigonal prisms, bicapped square anti­prisms, or 11-vertex polyhedra. The crystal structure of the title compound is also related to the structure types CaBe2Ge2 and W5Si3. It can be represented as a stacking of Gd-centred polyhedra of composition [GdSi9]. The Re atoms form infinite chains with an Re—Re distance of 2.78163 (5) Å and isolated squares with an Re—Re distance of 2.9683 (6) Å. PMID:25552967

In collaboration with industry, Idaho National Laboratory is investigating uranium silicide for use in future light water reactor fuels as a more accident resistant alternative to uranium oxide base fuels. Specifically this project was focused on producing uranium silicide (U3Si2) pellets by conventional powder metallurgy with a density greater than 94% of the theoretical density. This work has produced a process to consistently produce pellets with the desired density through careful optimization of the process. Milling of the U3Si2 has been optimized and high phase purity U3Si2 has been successfully produced. Results are presented from sintering studies and microstructural examinations that illustrate the need for a finely ground reproducible particle size distribution in the source powder. The optimized process was used to produce pellets for the Accident Tolerant Fuel-1 irradiation experiment. The average density of these pellets was 11.54 ± 0.06 g/cm3. Additional characterization of the pellets by scanning electron microscopy and X-ray diffraction has also been performed. Pellets produced in this work have been encapsulated for irradiation, and irradiation in the Advanced Test Reactor is expected soon.

In this study, we propose an ultra-facile approach to prepare a platinum silicide nanoparticle-modified tip apex (PSM tip) used for scanning Kelvin probe microscopy (SKPM). We combined a localized fluoride-assisted galvanic replacement reaction (LFAGRR) and atmospheric microwave annealing (AMA) to deposit a single platinum silicide nanoparticle with a diameter of 32 nm on the apex of a bare silicon tip of atomic force microscopy (AFM). The total process was completed in an ambient environment in less than 3 min. The improved potential resolution in the SKPM measurement was verified. Moreover, the resolution of the topography is comparable to that of a bare silicon tip. In addition, the negative charges found on the PSM tips suggest the possibility of exploring the use of current PSM tips to sense electric fields more precisely. The ultra-fast and cost-effective preparation of the PSM tips provides a new direction for the preparation of functional tips for scanning probe microscopy. PMID:26471480

Kinetic processes involving intermediate phase formation are often assumed to follow an Arrhenius temperature dependence. This behavior is usually inferred from limited data over narrow temperature intervals, where the exponential dependence is generally fully satisfied. However, direct evidence over wide temperature intervals is experimentally challenging and data are scarce. Here, we report a study of silicide formation between a 12 nm film of palladium and 15 nm of amorphous silicon in a wide range of heating rates, spanning six orders of magnitude, from 0.1 to 10{sup 5 }K/s, or equivalently more than 300 K of variation in reaction temperature. The calorimetric traces exhibit several distinct exothermic events related to interdiffusion, nucleation of Pd{sub 2}Si, crystallization of amorphous silicon, and vertical growth of Pd{sub 2}Si. Interestingly, the thickness of the initial nucleation layer depends on the heating rate revealing enhanced mass diffusion at the fastest heating rates during the initial stages of the reaction. In spite of this, the formation of the silicide strictly follows an Arrhenius temperature dependence over the whole temperature interval explored. A kinetic model is used to fit the calorimetric data over the complete heating rate range. Calorimetry is complemented by structural analysis through transmission electron microscopy and both standard and in-situ synchrotron X-ray diffraction.

The National Atomic Energy Commission (CNEA) of Argentine Republic owns and operates an installation for production of molybdenum-99 from fission products since 1985, and, since 1991, covers the whole national demand of this nuclide, carrying out a program of weekly productions, achieving an average activity of 13 terabecquerel per week. At present they are finishing an enlargement of the production plant that will allow an increase in the volume of production to about one hundred of terabecquerel. Irradiation targets are uranium/aluminium alloy with 90% enriched uranium with aluminium cladding. In view of international trends held at present for replacing high enrichment uranium (HEU) for enrichment values lower than 20 % (LEU), since 1990 the authors are in contact with the RERTR program, beginning with tests to adapt their separation process to new irradiation target conditions. Uranium silicide (U{sub 3}Si{sub 2}) was chosen as the testing material, because it has an uranium mass per volume unit, so that it allows to reduce enrichment to a value of 20%. CNEA has the technology for manufacturing miniplates of uranium silicide for their purposes. In this way, equivalent amounts of Molybdenum-99 could be obtained with no substantial changes in target parameters and irradiation conditions established for the current process with Al/U alloy. This paper shows results achieved on the use of this new target.

We present results of an unbiased structure search for stable ruthenium silicide compounds with various stoichiometries, using a recently developed technique that combines particle swarm optimization algorithms with first-principles calculations. Two experimentally observed structures of ruthenium silicides, RuSi (space group P2(1)3) and Ru2Si3 (space group Pbcn), are successfully reproduced under ambient pressure conditions. In addition, a stable RuSi2 compound with β-FeSi2 structure type (space group Cmca) was found. The calculations of the formation enthalpy, elastic constants, and phonon dispersions demonstrate the Cmca-RuSi2 compound is energetically, mechanically, and dynamically stable. The analysis of electronic band structures and densities of state reveals that the Cmca-RuSi2 phase is a semiconductor with a direct band gap of 0.480 eV and is stabilized by strong covalent bonding between Ru and neighboring Si atoms. On the basis of the Mulliken overlap population analysis, the Vickers hardness of the Cmca structure RuSi2 is estimated to be 28.0 GPa, indicating its ultra-incompressible nature. PMID:26576622

A single crystal of the title compound, the ternary silicide digadolinium trirhenium penta-silicide, Gd2Re3Si5, was isolated from an alloy of nominal composition Gd20Re30Si50 synthesized by arc melting and investigated by X-ray single-crystal diffraction. Its crystal structure belongs to the U2Mn3Si5 structure type. All atoms in the asymmetric lie on special positions. The Gd site has site symmetry m..; the two Mn atoms have site symmetries m.. and 2.22; the three Si atoms have site symmetries m.., ..2 and 4.. . The coordination polyhedra of the Gd atoms have 21 vertices, while those of the Re atoms are cubo-octa-hedra and 13-vertex polyhedra. The Si atoms are arranged as tricapped trigonal prisms, bicapped square anti-prisms, or 11-vertex polyhedra. The crystal structure of the title compound is also related to the structure types CaBe2Ge2 and W5Si3. It can be represented as a stacking of Gd-centred polyhedra of composition [GdSi9]. The Re atoms form infinite chains with an Re-Re distance of 2.78163 (5) Å and isolated squares with an Re-Re distance of 2.9683 (6) Å. PMID:25552967

In collaboration with industry, Idaho National Laboratory is investigating uranium silicide for use in future light water reactor fuels as a more accident resistant alternative to uranium oxide base fuels. Specifically this project was focused on producing uranium silicide (U3Si2) pellets by conventional powder metallurgy with a density greater than 94% of the theoretical density. This work has produced a process to consistently produce pellets with the desired density through careful optimization of the process. Milling of the U3Si2 has been optimized and high phase purity U3Si2 has been successfully produced. Results are presented from sintering studies and microstructural examinations that illustrate the need for a finely ground reproducible particle size distribution in the source powder. The optimized process was used to produce pellets for the Accident Tolerant Fuel-1 irradiation experiment. The average density of these pellets was 11.54 ±0.06 g/cm3. Additional characterization of the pellets by scaning electron microscopy and X-ray diffraction has also been performed. As a result, pellets produced in this work have been encapsulated for irradiation, and irradiation in the Advanced Test Reactor is expected soon.

This paper examines microstructure-property relationships in high-temperature directionally solidified (DS) in-situ composites based on Nb silicides, such as Nb{sub 3}Si and Nb{sub 5}Si{sub 3}. These in-situ composites are based on the Nb{sub 3}Si-Nb binary eutectic, and are alloyed with Ti. They were prepared using cold crucible Czochralski crystal growth. Ternary Nb-Ti-Si alloys with Ti concentrations from 9 to 45%, and Si concentrations from 10 to 25%, were directionally solidified to generate aligned two- and three-phase composites containing a Nb solid solution with Nb{sub 3}Si and Nb{sub 5}Si{sub 3} silicides. Fracture toughness values generally greater than 10 MPa{radical}m were measured in these composites. For a given Si concentration, the fracture toughness of the Ti-containing composites was increased {approximately}6 MPa{radical}m over that of the binary alloy composites. The effects of Si concentration, and a range of Nb:Ti ratios, on microstructure, phase equilibria, and fracture toughness were examined.

We report that the geometry of single-crystalline Si nanowires (NWs) prior to salicidation at 500 °C is the key factor controlling the phase, stress state, and electrical resistivity of the resulting Ni x Si y NWs of width less than 100 nm. This is a radical departure from previous observations of a single phase formation for nickel silicides generated from the silicidation of bulk Si substrates. The phase transition from NiSi for large NWs ( W Si NW = 250–450 nm) to Ni2Si for small NWs ( W Si NW = 70–100 nm) is well correlated with the observed volumetric expansion and electrical resistivity variation with the NW width. For the extremely small dimensions of Ni x Si y NWs, we propose that the preeminent, kinetics-based Zhang and d’Heurle model for salicidation be modified to a more thermodynamically-governed, volume-expansion dependent Ni x Si y phase formation. A novel, plastic deformation mechanism is proposed to explain the observed, geometry-dependent Ni x Si y NW phase formation that also strongly influences the electrical performance of the NWs.

We report in this paper the influence of film thickness on the material and magnetic properties of electroplated CoPt permanent magnets. Layers of CoPt magnets with film thicknesses ranging from 0.5 μm to 5 μm are deposited into photoresist molds (3.5 mm x 3.5 mm square and 5 μm x 50 μm arrays) on a (100)Si substrate coated with 10 nm/100 nm Ti/Cu adhesion/seed layer. Results show an unexpected reduction in magnetic properties for films below 2 μm thick. This effect is determined to be a consequence of metal-silicide reactions at the substrate interface during annealing leading to the formation of a non-magnetic layer at the interface. Subsequently, a TiN diffusion-barrier layer is added to inhibit the silicide reaction and thereby maintain strong magnetic properties (Hci ∼800 kA/m, Mr/Ms = 0.8) in micron- thick electroplated CoPt layers.

The differential scanning calorimetry (DSC) technique is employed to study the formation of different silicide compounds of Zr thin-film deposited on a 100 μm-thick Si (1 0 0) substrate by dc sputtering. A detailed analysis shows that silicide layers start growing at ∼246 °C that changes to stable ZrSi2 at 627 °C via some compounds with different stoichiometric ratios of Zr and Si. It is further observed that oxygen starts reacting with Zr at ∼540 °C but a stoichiometric ZrO2 film is formed after complete consumption of Zr metal at 857 °C. A further rise in temperature changes a part of ZrSi2 to Zr-Silicate. The synchrotron radiation-based grazing incidence x-ray diffraction and x-ray photoelectron spectroscopy studies also corroborate the above findings. Atomic force microscopy is also carried out on the samples. It is evident from the observations that an intermixing and nucleation of Zr and Si occur at lower temperature prior to the formation of the interfacial silicate layer. Zr-Silicate formation takes place only at a higher temperature.

This work demonstrates the fabrication of silicide/silicon based solar cell towards the development of low cost and environmental friendly photovoltaic technology. A heterostructure solar cells using metallic alpha phase (α-phase) aluminum alloyed iron silicide (FeSi(Al)) on n-type silicon is fabricated with an efficiency of 0.8%. The fabricated device has an open circuit voltage and fill-factor of 240 mV and 60%, respectively. Performance of the device was improved by about 7 fold to 5.1% through the interface engineering. The α-phase FeSi(Al)/silicon solar cell devices have promising photovoltaic characteristic with an open circuit voltage, short-circuit current and a fill factor (FF) of 425 mV, 18.5 mA/cm2, and 64%, respectively. The significant improvement of α-phase FeSi(Al)/n-Si solar cells is due to the formation p+-n homojunction through the formation of re-grown crystalline silicon layer (~5-10 nm) at the silicide/silicon interface. Thickness of the regrown silicon layer is crucial for the silicide/silicon based photovoltaic devices. Performance of the α-FeSi(Al)/n-Si solar cells significantly depends on the thickness of α-FeSi(Al) layer and process temperature during the device fabrication. This study will open up new opportunities for the Si based photovoltaic technology using a simple, sustainable, and los cost method.

This work develops a method for growing Ni-silicide/Si heterostructured nanowire arrays by glancing angle Ni deposition and solid state reaction on ordered Si nanowire arrays. Samples of ordered Si nanowire arrays were fabricated by nanosphere lithography and metal-induced catalytic etching. Glancing angle Ni deposition deposited Ni only on the top of Si nanowires. When the annealing temperature was 500°C, a Ni3Si2 phase was formed at the apex of the nanowires. The phase of silicide at the Ni-silicide/Si interface depended on the diameter of the Si nanowires, such that epitaxial NiSi2 with a {111} facet was formed at the Ni-silicide/Si interface in Si nanowires with large diameter, and NiSi was formed in Si nanowires with small diameter. A mechanism that is based on flux divergence and a nucleation-limited reaction is proposed to explain this phenomenon of size-dependent phase formation. PMID:23663726

Non-silicide PV cell structures were successfully applied to the photovoltaic (PV)-assisted UHF rectifier, which is one example realization of the “synergistic ambient energy harvesting” concept. Silicide blocking of PV cell area was experimentally verified to be effective for increasing photo-generated bias voltage, which resulted in the improved power conversion efficiency (PCE) of the rectifier by enhanced VTH compensation effect. Increase in both transparency of light and quantum efficiency of PV cells obtained by eliminating silicide layer affects the PCE improvement almost equally. 25.8% of PCE was achieved under the conditions of an RF input power of -20 dBm, a frequency of 920 MHz, an output load of 47 kΩ, and a typical indoor light irradiance level of 1 W/m2. In addition, when the non-silicide PV cell technique was applied to the voltage-boosted PV-cell structures, 32.1% peak PCE was achieved at 10 W/m2.

The results of the research process of producing metalized products by solid-phase reduction of iron using solid carbonaceous reducing agents. Thermodynamic modeling was carried out on the model of the unit the Fe-C-O and system with iron ore and coal. As a result of modeling the thermodynamic boundary reducing, oxidizing, and transition areas and the value of the ratio of carbon and oxygen in the system. Simulation of real systems carried out with the gas phase obtained in the pyrolys of coal. The simulation results allow to determine the optimal cost of coal required for complete reduction of iron ore from a given composition. The kinetics of the processes of solid-phase reduction of iron using coal of various technological brands. The paper describes experiments on effects of metal deoxidizer composition, component proportion, pelletizing mixture, particle size distribution of basic materials and flux on manganese recovering from oxides under direct melting.

A method of obtaining U/sup 233/ is described. An aqueous solution of neutriln irradiated thoriunn is treated by forming tberein a precipitate of manganese dioxide which carries and thus separates the Pa/sup 233/ from the solution. The carrier precipitate so formed is then dissolved in an acidic solution containing a reducing agent sufficiently electronegative to reduce the tetravalent manganese to the divalent state. Further purification of the Pa/sup 233/ may be obtained by forming another manganese dioxide carrier precipitate and subsequently dissolving it. Ater a sufficient number of such cycles have brought the Pa/sup 233/ to the desired purity, the solution is aged, allowing the formation ot U/sup 233/ by radioaetive decay. A manganese dioxide precipitate is then formed in the U/sup 233/ containing solution. This precipitate carries down any remaining Pa/sup 233/ thus leaving the separated U/sup 233/solution, from whieh it may be easily recovered.

... manganese compounds with sulfuric acid. It is also obtained as a byproduct in the manufacture of... dioxide in sulfuric acid, and the roasting of pyrolusite (MnO2) ore with solid ferrous sulfate and...

The presence of manganese in natural waters (>0.05 mg/L) degrades water-supply quality. A model was devised to predict the variation of manganese concentrations in river water released from an impoundment with the distance downstream. The model is one-dimensional and was calibrated using dissolved oxygen, biochemical oxygen demand, pH, manganese, and hydraulic data collected in the Duck River, Tennessee. The results indicated that the model can predict manganese levels under various conditions. The model was then applied to the Chattahoochee River, Georgia. Discrepancies between observed and predicted may be due to inadequate pH data, precipitation of sediment particles, unsteady flow conditions in the Chattahoochee River, inaccurate rate expressions for the los pH conditions, or their combinations.

This report describes the flow and processing of manganese within the U.S. economy in 1998 with emphasis on the extent to which manganese is recycled. Manganese was used mostly as an alloying agent in alloys in which it was a minor component. Manganese was recycled mostly within scrap of iron and steel. A small amount was recycled within aluminum used beverage cans. Very little manganese was recycled from materials being recovered specifically for their manganese content. For the United States in 1998, 218,000 metric tons of manganese was estimated to have been recycled from old scrap, of which 96% was from iron and steel scrap. Efficiency of recycling was estimated as 53% and recycling rate as 37%. Metallurgical loss of manganese was estimated to be about 1.7 times that recycled. This loss was mostly into slags from iron and steel production, from which recovery of manganese has yet to be shown economically feasible.

Objective This study examined the correlation between manganese exposure and manganese concentrations in different biomarkers. Methods Air measurement data and work histories were used to determine manganese exposure over a workshift and cumulative exposure. Toenail samples (n=49), as well as blood and urine before (n=27) and after (urine, n=26; blood, n=24) a workshift were collected. Results Toenail manganese, adjusted for age and dietary manganese, was significantly correlated with cumulative exposure in months 7-9, 10-12, and 7-12 before toenail clipping date, but not months 1-6. Manganese exposure over a work shift was not correlated with changes in blood nor urine manganese. Conclusions Toenails appeared to be a valid measure of cumulative manganese exposure 7 to 12 months earlier. Neither change in blood nor urine manganese appeared to be suitable indicators of exposure over a typical workshift. PMID:21494156

The observation of orthostatic hypotension in an index case of manganese toxicity lead to this prospective attempt to evaluate cardiovascular autonomic function and cognitive and emotional neurotoxicity in eight manganese alloy welders and machinists. The subjects consisted of a convenience sample consisting of an index case of manganese dementia, his four co-workers in a frog shop for gouging, welding, and grinding repair of high manganese railway track and a convenience sample of three mild steel welders with lesser manganese exposure also referred because of cognitive or autonomic symptoms. Frog shop air manganese samples 9.6--10 years before and 1.2--3.4 years after the diagnosis of the index case exceeded 1.0 mg/m{sup 3} in 29% and 0.2 mg/m{sup 3} in 62%. Twenty-four-hour electrocardiographic (Holter) monitoring was used to determine the temporal variability of the heartrate (RR{prime} interval) and the rates of change at low frequency and high frequency. MMPI and MCMI personality assessment and short-term memory, figure copy, controlled oral word association, and symbol digit tests were used.

The objective of this project was to understand and improve high-temperature structural properties of metal-silicide intermetallic alloys. Through research collaboration between the research team at West Virginia University (WVU) and Dr. J.H. Schneibel at Oak Ridge National Laboratory (ORNL), molybdenum silicide alloys were developed at ORNL and evaluated at WVU through atomistic modeling analyses, thermo-mechanical tests, and metallurgical studies. In this study, molybdenum-based alloys were ductilized by dispersing MgAl2O4 or MgO spinel particles. The addition of spinel particles is hypothesized to getter impurities such as oxygen and nitrogen from the alloy matrix with the result of ductility improvement. The introduction of fine dispersions has also been postulated to improve ductility by acting as a dislocation source or reducing dislocation pile-ups at grain boundaries. The spinel particles, on the other hand, can also act as local notches or crack initiation sites, which is detrimental to the alloy mechanical properties. Optimization of material processing condition is important to develop the desirable molybdenum alloys with sufficient room-temperature ductility. Atomistic analyses were conducted to further understand the mechanism of ductility improvement of the molybdenum alloys and the results showed that trace amount of residual oxygen may be responsible for the brittle behavior of the as-cast Mo alloys. For the alloys studied, uniaxial tensile tests were conducted at different loading rates, and at room and elevated temperatures. Thermal cycling effect on the mechanical properties was also studied. Tensile tests for specimens subjected to either ten or twenty thermal cycles were conducted. For each test, a follow-up detailed fractography and microstructural analysis were carried out. The test results were correlated to the size, density, distribution of the spinel particles and processing time. Thermal expansion tests were carried out using thermo

Oxidation of manganese (II) to manganese (III,IV) demands oxidants with very high redox potentials; consequently, manganese oxides are both excellent proxies for molecular oxygen and highly favorable electron acceptors when oxygen is absent. The first of these features results in manganese-enriched sedimentary rocks (manganese deposits, commonly Mn ore deposits), which generally correspond to the availability of molecular oxygen in Earth surface environments. And yet because manganese reduction is promoted by a variety of chemical species, these ancient manganese deposits are often significantly more reduced than modern environmental manganese-rich sediments. We document the impacts of manganese reduction and the mineral phases that form stable manganese deposits from seven sedimentary examples spanning from modern surface environments to rocks over 2 billion years old. Integrating redox and coordination information from synchrotron X-ray absorption spectroscopy and X-ray microprobe imaging with scanning electron microscopy and energy and wavelength-dispersive spectroscopy, we find that unlike the Mn(IV)-dominated modern manganese deposits, three manganese minerals dominate these representative ancient deposits: kutnohorite (CaMn(CO3)2), rhodochrosite (MnCO3), and braunite (Mn(III)6Mn(II)O8SiO4). Pairing these mineral and textural observations with previous studies of manganese geochemistry, we develop a paragenetic model of post-depositional manganese mineralization with kutnohorite and calcian rhodochrosite as the earliest diagenetic mineral phases, rhodochrosite and braunite forming secondarily, and later alteration forming Mn-silicates.

The water-oxidizing complex (WOC) within photosystem II (PSII) can be reconstituted with synthetic manganese complexes by a process called photoactivation; however, the key factors affecting the efficiency of synthetic manganese complexes in reconstitution of electron transport and oxygen evolution activity in manganese-depleted PSII remain unclear. In the present study, four complexes with different manganese coordination environments were used to reconstitute the WOC, and an interesting relationship was found between the coordination environment of the manganese atom in the complexes and their efficiency in restoring electron transport and oxygen evolution. If Mn(II) is coordinated to nitrogen atoms within the ligand, it can restore significant rates of electron transport and oxygen evolution; however, if the manganese atom is coordinated only to oxygen atoms instead of nitrogen atoms, it has no capability to restore electron transport and oxygen evolution. So, our results demonstrate that the capability of manganese complexes to reconstitute the WOC is mainly determined by the coordination between nitrogen atoms from ligands and the manganese atom. It is suggested from our results that the ligation between the nitrogen atom and the manganese atom within the manganese complex facilitates the photoligation of the manganese atom to histidyl residues on the apo-protein in manganese-depleted PSII during photoactivation. PMID:16791637

Oneida Lake, New York is a eutrophic freshwater lake known for its abundant manganese nodules and a dynamic manganese cycle. Temporal and spatial distribution of soluble and particulate manganese in the water column of the lake were analyzed over a 3-year period and correlated with other variables such as oxygen, pH, and temperature. Only data from 1988 are shown. Manganese is removed from the water column in the spring via conversion to particulate form and deposited in the bottom sediments. This removal is due to biological factors, as the lake Eh/pH conditions alone can not account for the oxidation of the soluble manganese Mn(II). During the summer months the manganese from microbial reduction moves from the sediments to the water column. In periods of stratification the soluble Mn(II) builds up to concentrations of 20 micromoles or more in the bottom waters. When mixing occurs, the soluble Mn(II) is rapidly removed via oxidation. This cycle occurs more than once during the summer, with each manganese atom probably being used several times for the oxidation of organic carbon. At the end of the fall, whole lake concentrations of manganese stabilize, and remain at about 1 micromole until the following summer, when the cycle begins again. Inputs and outflows from the lake indicate that the active Mn cycle is primarily internal, with a small accumulation each year into ferromanganese nodules located in the oxic zones of the lake.

Electrolytic manganese residue (EMR) is a solid waste found in filters after sulphuric acid leaching of manganese carbonate ore, which mainly contains manganese and ammonia nitrogen and seriously damages the ecological environment. This work demonstrated the use of electrokinetic (EK) remediation to remove ammonia nitrogen and manganese from EMR. The transport behavior of manganese and ammonia nitrogen from EMR during electrokinetics, Mn fractionation before and after EK treatment, the relationship between Mn fractionation and transport behavior, as well as the effects of electrolyte and pretreatment solutions on removal efficiency and energy consumption were investigated. The results indicated that the use of H2SO4 and Na2SO4 as electrolytes and pretreatment of EMR with citric acid and KCl can reduce energy consumption, and the removal efficiencies of manganese and ammonia nitrogen were 27.5 and 94.1 %, respectively. In these systems, electromigration and electroosmosis were the main mechanisms of manganese and ammonia nitrogen transport. Moreover, ammonia nitrogen in EMR reached the regulated level, and the concentration of manganese in EMR could be reduced from 455 to 37 mg/L. In general, the electrokinetic remediation of EMR is a promising technology in the future. PMID:26062467

Systems, devices, and methods combine thermally stable reactant materials and aqueous solutions to generate hydrogen and a non-toxic liquid by-product. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Springs and other pressurization mechanisms pressurize and deliver an aqueous solution to the reaction. A check valve and other pressure regulation mechanisms regulate the pressure of the aqueous solution delivered to the reactant fuel material in the reactor based upon characteristics of the pressurization mechanisms and can regulate the pressure of the delivered aqueous solution as a steady decay associated with the pressurization force. The pressure regulation mechanism can also prevent hydrogen gas from deflecting the pressure regulation mechanism.

Interest in the use of EPMA at low voltage has grown considerably in recent years, mainly because of the availability of electron-beam instruments equipped with field-emission guns. However, EPMA at low voltage is marred by both experimental and analytical problems which may affect the accuracy of quantitative results. In the case of the analysis of transition elements, both the emission and absorption of X-rays are still poorly understood when they originate from electron transitions involving the partially filled 3d-shell. This is the case for the most intense Lα (L3-M5 transition) and Lβ (L2-M4 transition) lines. In this communication, we point out anomalies which appear to afflict the accuracy of EPMA of Ni-silicides using the Ni-Lα X-ray line and we discuss possible solutions.

Rare-earth induced layered structures on the Si(111) surface are investigated by a combined approach consisting of ab initio thermodynamics, electron and x-ray diffraction experiments, angle-resolved photoelectron spectroscopy, and scanning tunneling microscopy. Our density functional theory calculations predict the occurrence of structures with different periodicity, depending on the rare-earth availability. Microscopic structural models are assigned to the different silicide phases on the basis of stability criteria. The thermodynamically stable theoretical models are then employed to interpret the experimental results. The agreement between the simulated and measured scanning tunneling microscopy images validates the proposed structural models. The electronic properties of the surfaces are discussed on the basis of the calculated electronic band structure and photoelectron spectroscopy data.

We have discovered a method to promote the growth of Mn silicide nanowires on the Si(001) at 450° C. Deposition of sub-monolayer quantities of Mn onto a Si(001) surface with a high density of Bi nanolines results in the formation of nanowires, 5-10 nm wide, and up to 600 nm long. These nanowires are never formed if the same growth procedure is followed in the absence of the Bi nanolines. The Haiku core of the Bi nanoline is known to induce short-range stress in the surrounding silicon surface, straining neighbouring dimers, and repelling step edges. We discuss the possible mechanisms for this effect, including the effect of the Bi nanolines on the surface stress tensor and alteration of the available diffusion channels on the surface. This research was partially supported by the Ministry of Education, Science, Sports and Culture, Grant-in-Aid for Scientific Research, the Iketani Science and Technology Foundation.

This paper presents the growth mechanism of a monocrystalline silicide quantum dot superlattices (QDSL) grown by reduced pressure chemical vapor deposition (RPCVD). QDSL are made of TiSi2-based nanodots scattered in a p-doped Si90Ge10 matrix. It is the first time that the growth of a p-type monocrystalline QDSL is presented. We focus here on the growth mechanisms of QDSL and the influence of nanostructuration on their thermal properties. Thus, the dots surface deposition, the dots embedding mechanisms and the final QDSL growths are studied. The crystallographic structures and chemical properties are presented, as well as the thermal properties. It will be shown that some specific mechanisms occur such as the formation of self-formed quantum well superlattices and the dopant accumulation near the quantum dots. Finally, a slight decrease of the QDSL thermal conductivity has been measured compared to the reference sample.

Results are presented of a program of research to develop a reliable, high performance, fused slurry silicide coating for the Ta-10W alloy. The effort was directed toward developing new and improved formulations for use at 2600 to 2800 F (1700 to 1811 K) in an atmospheric reentry thermal protection system with a 100-mission capability. Based on a thorough characterization of isothermal and cyclic oxidation behavior, bend transition temperatures, room- and elevated-temperature tensile properties, and creep behavior, a 2.5 Mn-33Ti-64.5Si coating (designated MTS) provides excellent protection for the Ta-10W alloy in simulated reentry environments. An extensive analysis of the oxidation behavior and characteristics of the MTS coating in terms of fundamental mechanisms also is presented.

The growth kinetics of platinum silicides have been studied on four substrate categories: single-crystal, amorphous, undoped polycrystalline, and phosphorus-doped (8×1020 at./cm3) polycrystalline silicon. The sequential growth of Pt2Si and PtSi were analyzed by Rutherford backscattering spectroscopy (RBS), Seeman-Bohlin x-ray diffraction, and cross-section transmission electron microscopy. Phosphorus depth profiles were measured by secondary ion mass spectroscopy (SIMS). Our results conclude that the activation energies for the growth of Pt2Si and PtSi are not affected by substrate crystallinity and doping of phosphorus. Analysis of the phosphorus profile by SIMS clearly showed that phosphorus atoms are segregated near the interface between PtSi and polycrystalline silicon, but not at the Pt2Si/polycrystalline silicon interface.

The friction and wear properties of several refractory compound coatings were examined. These compounds were applied to 440 C bearing steel surfaces by radiofrequency (RF) sputtering. The refractory compounds were the titanium and molybdenum borides, the titanium and molybdenum silicides, and the titanium, molybdenum, and boron carbides. Friction testing was done with a pin-on-disk wear apparatus at loads from 0.1 to 5.0 newtons. Generally, the best wear properties were obtained when the coatings were bias sputtered onto 440 C disks that had been preoxidized. Adherence was improved because of the better bonding of the coatings to the iron oxide formed during preoxidation. As a class the carbides provided wear protection to the highest loads. Titanium boride coatings provided low friction and good wear properties to moderate loads.

Metal silicide Schottky barrier monolithic mosaic sensors have been developed for SWIR and thermal imaging applications. The first generation Pd2Si Schottky barrier sensors operated between 120-140K have a cut-off wavelength of 3.5 microns and quantum efficiency between 1 and 8% in the 1-2.4 micron spectral band. PtSi Schottky barrier sensors without AR-coating operated at 80K have a cut-off wavelength around 6 microns and quantum efficiency between 4.1 and 0.3% in the 3 to 5.5 micron range. The radiometric characteristics, response uniformity, dynamic range, spectral response, dark current and temporal response are described. The application of the technology in satellite-borne multispectral imaging is discussed. SWIR and thermal images are illustrated.

Systems, devices, and methods combine reactant materials and aqueous solutions to generate hydrogen. The reactant materials can sodium silicide or sodium silica gel. The hydrogen generation devices are used in fuels cells and other industrial applications. One system combines cooling, pumping, water storage, and other devices to sense and control reactions between reactant materials and aqueous solutions to generate hydrogen. Multiple inlets of varied placement geometries deliver aqueous solution to the reaction. The reactant materials and aqueous solution are churned to control the state of the reaction. The aqueous solution can be recycled and returned to the reaction. One system operates over a range of temperatures and pressures and includes a hydrogen separator, a heat removal mechanism, and state of reaction control devices. The systems, devices, and methods of generating hydrogen provide thermally stable solids, near-instant reaction with the aqueous solutions, and a non-toxic liquid by-product.

The thermoelectric properties of magnesium silicide samples prepared by Vacuum Plasma Spray (VPS) are compared with those made from the conventional hot press method using the same feedstock powder. Thermal conductivity, electrical conductivity, Seebeck coefficient, and figure of merit are characterized from room temperature to 700 K. X-ray diffraction and scanning electron microscopy of the samples are obtained to assess how phase and microstructure influence the thermoelectric properties. Carrier concentration and Hall mobility are obtained from Hall Effect measurements, which provide further insight into the electrical conductivity and Seebeck coefficient mechanisms. Low-temperature electrical conductivity measurements suggest a 3D variable range hopping effect in the samples. VPS samples achieved a maximum ZT = 0.16 at 700 K, which is around 30% of the hot press sample ZT = 0.55 at 700 K using the same raw powder. The results suggest that thermal spray is a potential deposition technique for thermoelectric materials.

Nickel-manganese alloy electrodeposits from an electrolyte containing more manganese ion than previously used is being evaluated at two bath operating temperatures with a great variety of pulse plating conditions. Saccharine was added as a stress reducing agent for the electroforming of several of the samples with highest manganese content. All specimens for mechanical property testing have been produced but are not through the various heat treatments as yet. One of the heat treatment will be at 343 C (650 F), the temperature at which the MCC outer electroformed nickel shell is stress relieved. A number of retainer specimens from prior work have been tested for hardness before and after heat treatment. There appears to be a fairly good correlation between hardness and mechanical properties. Comparison of representative mechanical properties with hardnesses are made for nickel-manganese electrodeposits and nickel-cobalt-manganese deposits.

A fungi strain named Fusarium sp. was isolated from manganese-electrolysed slag by using a gradient dilution spread plate method, identified by 26S RNA sequence analysis and phylogenetic tree analysis, and explored for the bioleaching capacity to manganese (II) from manganese-electrolysed slag in liquid mineral medium under different environmental conditions, including system temperature, incubator rotation speed and initial pH value. DNA sequence and phylogenetic analysis indicated the name of this fungi strain, that is, Fusarium sp., and higher bioleaching efficiencies (71.6%) of manganese by this fungi were observed when the bioleaching was carried out under the optimized conditions as follows: contact time: 72 h; system temperature: 28 degrees C; inoculums concentration: 2% (v/v); incubator rotation speed: 150 rpm; pH 4.0. Because of its low cost, environment friendliness and better efficiency, the bioleaching technique will have a significant impact on manganese-electrolysed slag pollution mitigation. PMID:22856303

Parkinsonism is a clinical syndrome consisting of tremor, bradykinesia, rigidity, gait, balance problems, in addition to various non-motor symptoms. There are many causes of parkinsonism such as neurodegenerative disease, drugs, vascular causes, structural lesions, infections, and toxicants. Parkinson's disease, or idiopathic parkinsonism, is the most common form of parkinsonism observed in the clinic. There is degeneration of the substantia nigra, pars compacta, which results in loss of striatal dopamine. Parkinson's disease is a slowly progressive condition in which there is a dramatic and sustained responsiveness to levodopa therapy. Manganese is an essential trace element that can be associated with neurotoxicity. Hypermanganism can occur in a variety of clinical settings. The clinical symptoms of manganese intoxication include non-specific complaints, neurobehavioral changes, parkinsonism, and dystonia. Although the globus pallidus is the main structure of damage, other basal ganglia areas can also be involved. MRI scans may show globus pallidus changes during (and for a short period after) exposure. Fluorodopa PET scans that assess the integrity of the substantia nigra dopaminergic system are abnormal in Parkinson's disease. However, these scans re-reported to be normal in a few cases studied with manganese-induced parkinsonism. The parkinsonism due to manganese may have some clinical features that occur less commonly in Parkinson's disease, such as kinetic tremor, dystonia, specific gait disturbances, and early mental, balance and speech changes. The clinical signs tend to be bilateral whereas Parkinson's disease begins on one side of the body. Patients with manganese-induced parkinsonism may be younger at the onset of the disease than with Parkinson's disease. Lastly, there appears to be a lack of response to levodopa therapy in manganese-induced parkinsonism. In summary it may be possible to differentiate manganese-induced parkinsonism from Parkinson

Manganese (Mn)-induced Parkinsonism has been well documented; however, little attention has been devoted to Mn-induced cardiovascular dysfunction. This review summarizes literature data from both animal and human studies on Mn’s effect on cardiovascular function. Clinical and epidemiological evidence suggests that the incidence of abnormal electrocardiogram (ECG) is significantly higher in Mn-exposed workers than that in the control subjects. The main types of abnormal ECG include sinus tachycardia, sinus bradycardia, sinus arrhythmia, sinister megacardia, and ST-T changes. The accelerated heartbeat and shortened P-R interval appear to be more prominent in female exposed workers than in their male counterparts. Mn-exposed workers display a mean diastolic blood pressure that is significantly lower than that of the control subjects, especially in the young and female exposed workers. Animal studies indicate that Mn is capable of quickly accumulating in heart tissue, resulting in acute or sub-acute cardiovascular disorders, such as acute cardiodepression and hypotension. These toxic outcomes appear to be associated with Mn-induced mitochondrial damage and interaction with the calcium channel in the cardiovascular system. PMID:16382172

The "cradle to grave" concept of managing chemicals and wastes has been a descriptive analogy of proper environmental stewardship since the 1970s. The concept incorporates environmentally sustainable product choices-such as metal alloys utilized steel products which civilization is dependent upon. Manganese consumption is related to the increasing production of raw steel and upgrading ferroalloys. Nonferrous applications of manganese include production of dry-cell batteries, plant fertilizer components, animal feed and colorant for bricks. The manganese ore (high grade 35% manganese) production world wide is about 6 million ton/year and electrolytic manganese metal demand is about 0.7 million ton/year. The total manganese demand is consumed globally by industries including construction (23%), machinery (14%), and transportation (11%). Manganese is recycled within scrap of iron and steel, a small amount is recycled within aluminum used beverage cans. Recycling rate is 37% and efficiency is estimated as 53% [Roskill Metals and Minerals Reports, January 13, 2005. Manganese Report: rapid rise in output caused by Chinese crude steel production. Available from: http://www.roskill.com/reports/manganese.]. Environmentally sustainable management choices include identifying raw material chemistry, utilizing clean production processes, minimizing waste generation, recycling materials, controlling occupational exposures, and collecting representative environmental data. This paper will discuss two electrolytically produced manganese metals, the metal production differences, and environmental impacts cited to date. The two electrolytic manganese processes differ due to the addition of sulfur dioxide or selenium dioxide. Adverse environmental impacts due to use of selenium dioxide methodology include increased water consumption and order of magnitude greater solid waste generation per ton of metal processed. The use of high grade manganese ores in the electrolytic process also

Manganese-oxidizing heterotrophic bacteria were found to comprise a significant proportion of the bacterial community of Lake Washington (Seattle, Wash.) and Lake Virginia (Winter Park, Fla.). Identification of these freshwater bacteria showed that members of a variety of genera are capable of oxidizing manganese. Isolates maintained in the laboratory spontaneously lost the ability to oxidize manganese. A direct correlation was found between the presence of plasmid DNA and the ability of the organism to oxidize manganese. PMID:16346084

We reported a simple method to grow good-quality CoSi 2 film by using Si cap technology and introducing moderate Ni. First, a cobalt layer of ∼15 nm with a Si cap layer with a different thickness deposited onto the Si surface with a thin silicon oxide buffer is applied to investigate the formation of CoSi 2 by ex situ rapid thermal annealing. It was found that a 13 nm thick Si cap layer could significantly improve the crystal quality of oxide-mediated CoSi 2 film. Setting the Si cap thickness at 13 nm, we revealed that introduction of Ni can further improve the crystal quality of the silicide film in comparison to the pure Co silicide, and a ratio of Ni to Co at round 1:8 causes the lowest sheet resistance, ∼5 Ω/sq.

Manganese oxides are often highly reactive and easily reduced, both abiotically, by a variety of inorganic chemical species, and biologically during anaerobic respiration by microbes. To evaluate the reaction mechanisms of these different reduction routes and their potential lasting products, we measured the sequence progression of microbial manganese(IV) oxide reduction mediated by chemical species (sulfide and ferrous iron) and the common metal-reducing microbe Shewanella oneidensis MR-1 under several endmember conditions, using synchrotron X-ray spectroscopic measurements complemented by X-ray diffraction and Raman spectroscopy on precipitates collected throughout the reaction. Crystalline or potentially long-lived phases produced in these experiments included manganese(II)-phosphate, manganese(II)-carbonate, and manganese(III)-oxyhydroxides. Major controls on the formation of these discrete phases were alkalinity production and solution conditions such as inorganic carbon and phosphate availability. The formation of a long-lived Mn(III) oxide appears to depend on aqueous Mn(2+) production and the relative proportion of electron donors and electron acceptors in the system. These real-time measurements identify mineralogical products during Mn(IV) oxide reduction, contribute to understanding the mechanism of various Mn(IV) oxide reduction pathways, and assist in interpreting the processes occurring actively in manganese-rich environments and recorded in the geologic record of manganese-rich strata. PMID:27018915

This work demonstrates the fabrication of silicide/silicon based solar cell towards the development of low cost and environmental friendly photovoltaic technology. A heterostructure solar cells using metallic alpha phase (α-phase) aluminum alloyed iron silicide (FeSi(Al)) on n-type silicon is fabricated with an efficiency of 0.8%. The fabricated device has an open circuit voltage and fill-factor of 240 mV and 60%, respectively. Performance of the device was improved by about 7 fold to 5.1% through the interface engineering. The α-phase FeSi(Al)/silicon solar cell devices have promising photovoltaic characteristic with an open circuit voltage, short-circuit current and a fill factor (FF) of 425 mV, 18.5 mA/cm2, and 64%, respectively. The significant improvement of α-phase FeSi(Al)/n-Si solar cells is due to the formation p+−n homojunction through the formation of re-grown crystalline silicon layer (~5–10 nm) at the silicide/silicon interface. Thickness of the regrown silicon layer is crucial for the silicide/silicon based photovoltaic devices. Performance of the α-FeSi(Al)/n-Si solar cells significantly depends on the thickness of α-FeSi(Al) layer and process temperature during the device fabrication. This study will open up new opportunities for the Si based photovoltaic technology using a simple, sustainable, and los cost method. PMID:26632759

Risk assessments of manganese by inhalation or oral routes of exposure typically acknowledge the duality of manganese as an essential element at low doses and a toxic metal at high doses. Previously, however, risk assessors were unable to describe manganese pharmacokinetics quant...

This invention relates to electrodes for non-aqueous lithium cells and batteries with silver manganese oxide positive electrodes, denoted AgxMnOy, in which x and y are such that the manganese ions in the charged or partially charged electrodes cells have an average oxidation state greater than 3.5. The silver manganese oxide electrodes optionally contain silver powder and/or silver foil to assist in current collection at the electrodes and to improve the power capability of the cells or batteries. The invention relates also to a method for preparing AgxMnOy electrodes by decomposition of a permanganate salt, such as AgMnO4, or by the decomposition of KMnO4 or LiMnO4 in the presence of a silver salt.

Microbes that couple growth to the reduction of manganese could play an important role in the biogeochemistry of certain anaerobic environments. Such a bacterium, Alteromonas putrefaciens MR-1, couples its growth to the reduction of manganese oxides only under anaerobic conditions. The characteristics of this reduction are consistent with a biological, and not an indirect chemical, reduction of manganese, which suggest that this bacterium uses manganic oxide as a terminal electron acceptor. It can also utilize a large number of other compounds as terminal electron acceptors; this versatility could provide a distinct advantage in environments where electron-acceptor concentrations may vary.

Ultrathin Ni, Co, and Pt films, each no more than 4 nm in thickness, as well as their various combinations are employed to investigate the competing growth of epitaxial Co{sub 1-y}Ni{sub y}Si{sub 2} films against polycrystalline Pt{sub 1-z}Ni{sub z}Si. The phase formation critically affects the morphological stability of the resulting silicide films, with the epitaxial films being superior to the polycrystalline ones. Any combination of those metals improves the morphological stability with reference to their parent individual metal silicide films. When Ni, Co, and Pt are all included, the precise initial location of Pt does little to affect the final phase formation in the silicide films and the epitaxial growth of Co{sub 1-x}Ni{sub x}Si{sub 2} films is always perturbed, in accordance to thermodynamics that shows a preferential formation of Pt{sub 1-z}Ni{sub z}Si over that of Co{sub 1-y}Ni{sub y}Si{sub 2}.

Pt-doped Ni (NiPt) silicide agglomeration in terms of NiSi crystal orientation, Pt segregation at the NiSi/Si interface, and residual stress is studied for the first time. In the annealing of Ni monosilicide (NiSi), the growth of NiSi grains whose NiSi b-axes are aligned normal to Si(001) [NiSi(010) ∥ Si(001)] with increasing Pt segregation at the NiSi/Si interface owing to a high annealing temperature was observed. The residual stress in NiSi(010) ∥ Si(001) grains also increases with increasing annealing temperature. Furthermore, the recrystallization of NiSi(010) ∥ Si(001) grains with increasing residual stress continues through additional annealing after NiSi formation. After the annealing of NiSi(010) ∥ Si(001) grains with their strain at approximately 2%, the start of NiPt silicide agglomerates accompanied by stress relaxation was observed. This preferential recrystallization of NiSi(010) ∥ Si(001) grains with increasing residual stress is considered to enhance the NiPt silicide agglomeration.

The study concerned a detailed microstructural investigation of nano-borides (Cr2B and Ni3B) and nano-silicide (Ni2Si) dispersed γ-nickel composite coating on AISI 304 stainless steel by HVOF spray deposition of the NiCrBSi precursor powder and subsequent laser surface melting. A continuous wave diode laser with an applied power of 3 kW and scan speed of 20 mm/s in argon shroud was employed. The characterization of the surface in terms of microstructure, microtexture, phases, and composition were carried out and compared with the as-coated (high-velocity oxy-fuel sprayed) surface. Laser surface melting led to homogenization and refinement of microstructures with the formation of few nano-silicides of nickel along with nano-borides of nickel and chromium (Ni3B, Cr2B, and Cr2B3). A detailed microtexture analysis showed the presence of no specific texture in the as-sprayed and laser-melted surface of Cr2B and Ni3B phases. The average microhardness was improved to 750-900 VHN as compared to 250 VHN of the as-received substrate. Laser surface melting improved the microhardness further to as high as 1400 VHN due to refinement of microstructure and the presence of silicides.

The effective charges of Si in both magnesium (Mg{sub 2}Si) and calcium silicides (CaSi and Ca{sub 2}Si) have been investigated by measuring high-resolution Si K{alpha} x-ray fluorescence spectra. CaSi showed small but positive chemical shifts (+0.03 eV), while the chemical shift of Mg{sub 2}Si was negative (-0.14 eV), as expected from their electronegativity (Ca: 1.00; Mg: 1.31; Si: 1.90). The similarity of the chemical shift for the Fe silicides and the calculations for the free single Si atom suggested that the effective charge of Si for CaSi was positive. From the observations the effective charges on Si in CaSi and Mg{sub 2}Si were estimated to be +0.1 and -0.3 electrons. The discrete variation Hatree-Fock-Slater calculations for Mg{sub 2}Si and CaSi also showed opposite chemical shifts and effective charges: -0.09 eV and -0.35 electrons for Mg{sub 2}Si and +0.09 eV and +0.26 electrons for CaSi, respectively. The composition of the nearest-neighbor atoms of Si, which are Si in CaSi and Mg in Mg{sub 2}Si, cause the opposite effective charges between the two silicides.

Carbon steels or low-alloy steels used in utility boilers, heat exchangers, petrochemical plants and coal gasification systems are subjected to high temperature corrosion attack such as oxidation, sulfidation and hot corrosion. The pack cementation coating process has proven to be an economical and effective method to enhance the corrosion resistance by modifying the surface composition of steels. With the aid of a computer program, STEPSOL, pack cementation conditions to produce a ferrite Cr-Al diffusion coating on carbon-containing steels by using elemental Cr and Al powders have been calculated and experimentally verified. The cyclic oxidation kinetics for the Cr-Al coated steels are presented. Chromium silicide can maintain high oxidation resistance up to 1100{degrees}C by forming a SiO{sub 2} protective scale. Previous studies at Ohio State University have shown that the cyclic oxidation resistance of MOSi{sub 2} and TiSi{sub 2} can be further improved by Ge addition introduced during coating growth. The halide-activated pack cementation process was modified to produce a Ge-doped silicide diffusion coating in a single processing step for the ORNL-developed Cr-Nb advanced intermetallic alloy. The oxidation behavior of the silicide-coated Cr-Nb alloy was excellent: weight gain of about 1 mg/cm{sup 2} upon oxidation at 1100{degrees}C in air for 100 hours.

Manganese superoxide dismutase is an important antioxidant defense metalloenzyme that protects cells from damage by the toxic oxygen metabolite, superoxide free radical, formed as an unavoidable by-product of aerobic metabolism. Many years of research have gone into understanding how the metal cofactor interacts with small molecules in its catalytic role. In contrast, very little is presently known about how the protein acquires its metal cofactor, an important step in the maturation of the protein and one that is absolutely required for its biological function. Recent work is beginning to provide insight into the mechanisms of metal delivery to manganese superoxide dismutase in vivo and in vitro. PMID:19699328

In the current work, silicide coatings were produced on the Nb alloy (Nb-1 pct Zr-0.1 pct C) using the halide activated pack cementation (HAPC) technique. Coating parameters (temperature and time) were optimized to produce a two-layer (Nb5Si3 and NbSi2) coating on the Nb alloy. Subsequently, the oxidation behavior of the Nb alloy (Nb-1 pct Zr-0.1 pct C) and silicide-coated Nb alloy was studied using thermogravimetric analysis (TGA) and isothermal weight gain oxidation experiments. Phase identification and morphological examinations were carried out using X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. TGA showed that the Nb alloy started undergoing accelerated oxidation at and above 773 K (500 °C). Isothermal weight gain experiments carried out on the Nb alloy under air environment at 873 K (600 °C) up to a time period of 16 hours exhibited a linear growth rate law of oxidation. In the case of silicide-based coatings, TGA showed that oxidation resistance of silicide coatings was retained up to 1473 K (1200 °C). Isothermal weight gain experiments on the silicide coatings carried out at 1273 K (1000 °C) in air showed that initially up to 8 hours, the weight of the sample increased, and beyond 8 hours the weight of the sample remained constant. The oxide phases formed on the bare samples and on the coated samples during oxidation were found to be Nb2O5 and a mixture of SiO2 and Nb2O5 phases, respectively. SEM showed the formation of nonprotective oxide layer on the bare Nb alloy and a protective (adherent, nonporous) oxide layer on silicide-coated samples. The formation of protective SiO2 layer on the silicide-coated samples greatly improved the oxidation resistance at higher temperatures.

Extracellular manganese peroxidase and laccase activities were detected in cultures of Dichomitus squalens (Polyporus anceps) under conditions favoring lignin degradation. In contrast, neither extracellular lignin peroxidase nor aryl alcohol oxidase activity was detected in cultures grown under a wide variety of conditions. The mineralization of {sup 14}C-ring-, -side chain-, and -methoxy-labeled synthetic guaiacyl lignins by D. squalens and the expression of extracellular manganese peroxidase were dependent on the presence of Mn(II), suggesting that manganese peroxidase is an important component of this organism's lignin degradation system. The expression of laccase activity was independent of manganese. In contrast to previous findings with Phanero-chaete chrysosporium, lignin degradation by D. squalens proceeded in the cultures containing excess carbon and nitrogen.

In order to utilize nanostructured materials for potential solar and other energy-harvesting applications, scalable synthetic techniques for these materials must be developed. Herein we use a vapor phase conversion approach to synthesize nanowire (NW) arrays of semiconducting barium silicide (BaSi2) in high yield for the first time for potential solar applications. Dense arrays of silicon NWs obtained by metal-assisted chemical etching were converted to single-crystalline BaSi2 NW arrays by reacting with Ba vapor at about 930 °C. Structural characterization by X-ray diffraction and high-resolution transmission electron microscopy confirm that the converted NWs are single-crystalline BaSi2. The optimal conversion reaction conditions allow the phase-pure synthesis of BaSi2 NWs that maintain the original NW morphology, and tuning the reaction parameters led to a controllable synthesis of BaSi2 films on silicon substrates. The optical bandgap and electrochemical measurements of these BaSi2 NWs reveal a bandgap and carrier concentrations comparable to previously reported values for BaSi2 thin films.In order to utilize nanostructured materials for potential solar and other energy-harvesting applications, scalable synthetic techniques for these materials must be developed. Herein we use a vapor phase conversion approach to synthesize nanowire (NW) arrays of semiconducting barium silicide (BaSi2) in high yield for the first time for potential solar applications. Dense arrays of silicon NWs obtained by metal-assisted chemical etching were converted to single-crystalline BaSi2 NW arrays by reacting with Ba vapor at about 930 °C. Structural characterization by X-ray diffraction and high-resolution transmission electron microscopy confirm that the converted NWs are single-crystalline BaSi2. The optimal conversion reaction conditions allow the phase-pure synthesis of BaSi2 NWs that maintain the original NW morphology, and tuning the reaction parameters led to a controllable

Uranium silicide (U3Si2) fuel has higher thermal conductivity and higher uranium density, making it a promising candidate for the accident-tolerant fuel (ATF) used in light water reactors (LWRs). However, previous studies on the fuel performance of U3Si2, including both experimental and computational approaches, have been focusing on the irradiation conditions in research reactors, which usually involve low operation temperatures and high fuel burnups. Thus, it is important to examine the fuel performance of U3Si2 at typical LWR conditions so as to evaluate the feasibility of replacing conventional uranium dioxide fuel with this silicide fuel material. As in-reactor irradiation experiments involve significant time and financial cost, it is appropriate to utilize modeling tools to estimate the behavior of U3Si2 in LWRs based on all those available research reactor experimental references and state-of-the-art density functional theory (DFT) calculation capabilities at the early development stage. Hence, in this report, a comprehensive investigation of the fission gas swelling behavior of U3Si2 at LWR conditions is introduced. The modeling efforts mentioned in this report was based on the rate theory (RT) model of fission gas bubble evolution that has been successfully applied for a variety of fuel materials at devious reactor conditions. Both existing experimental data and DFT-calculated results were used for the optimization of the parameters adopted by the RT model. Meanwhile, the fuel-cladding interaction was captured by the coupling of the RT model with simplified mechanical correlations. Therefore, the swelling behavior of U3Si2 fuel and its consequent interaction with cladding in LWRs was predicted by the rate theory modeling, providing valuable information for the development of U3Si2 fuel as an accident

Transition metals such as manganese are essential nutrients for both pathogen and host. Vertebrates exploit this necessity to combat invading microbes by restricting access to these critical nutrients, a defense known as nutritional immunity. During infection, the host uses several mechanisms to impose manganese limitation. These include removal of manganese from the phagolysosome, sequestration of extracellular manganese, and utilization of other metals to prevent bacterial acquisition of manganese. In order to cause disease, pathogens employ a variety of mechanisms that enable them to adapt to and counter nutritional immunity. These adaptations include, but are likely not limited to, manganese-sensing regulators and high-affinity manganese transporters. Even though successful pathogens can overcome host-imposed manganese starvation, this defense inhibits manganese-dependent processes, reducing the ability of these microbes to cause disease. While the full impact of host-imposed manganese starvation on bacteria is unknown, critical bacterial virulence factors such as superoxide dismutases are inhibited. This chapter will review the factors involved in the competition for manganese at the host-pathogen interface and discuss the impact that limiting the availability of this metal has on invading bacteria. PMID:27571690

Manganese recovery from industrial ore processing waste by means of leaching with sulfuric acid was the objective of this study. Experimental conditions were optimized by multivariate experimental design approaches. In order to study the factors affecting leaching, a screening step was used involving a full factorial design with central point for three variables in two levels (2(3)). The three variables studied were leaching time, concentration of sulfuric acid and sample amount. The three factors screened were shown to be relevant and therefore a Doehlert design was applied to determine the best working conditions for leaching and to build the response surface. By applying the best leaching conditions, the concentrations of 12.80 and 13.64 %w/w of manganese for the global sample and for the fraction -44 + 37 μm, respectively, were found. Microbeads of chitosan were tested for removal of leachate acidity and recovering of soluble manganese. Manganese recovery from the leachate was 95.4%. Upon drying the leachate, a solid containing mostly manganese sulfate was obtained, showing that the proposed optimized method is efficient for manganese recovery from ore tailings. PMID:25284800

The document evaluates data on occurrence, sources, and transport of manganese in the environment and data on metabolism, pharmacokinetics, laboratory toxicological and epidemiologic studies to determine the nature and dose response relationship of potential health effects on humans. Nationwide air sampling data indicate that mean manganese concentrations have declined from 0.11 micrograms per cu. m. in 1953-1957 to 0.033 micrograms per cu. m. in 1982. The effects of major concern to humans exposed to manganese are on neurological and on pulmonary function. The CNS effects have been observed in humans at exposure levels above 5 mg/cu. m. and are incapacitating and generally irreversible. Data are equivocal between 1 and 5 mg/cu. m. but suggest decreased prevalence. There are no reports of these effects below 0.3 mg/cu. m. exposure. Pneumonia and chronic bronchitis occur at levels which are associated with neurological effects. Reduced lung function has been reported in children exposed to an estimated 3-11 micrograms per cu. m. from emission of a ferromanganese plant. However, studies of workers exposed to 40 micrograms per cu. m. did not show respiratory symptoms. Animal studies qualitatively support pulmonary effects of manganese exposure. Respiratory symptoms occur at lower levels than neurological symptoms and are therefore considered to be the critical effect based on available data.

Deposits of manganese ore have been found in five of the six provinces of Cuba and have been reported from the sixth. Only Oriente and Pinar del Rio provinces have more than a few known deposits and only the deposits of Oriente have yielded any appreciable amount of ore.

Manganese, the second most abundant transition metal in the earth's crust, exists in a number of oxidation states, among which the II, III, and IV oxidation states are of greatest environmental importance. Produced through microbial activity, manganese oxides help to mediate redox reactions with organic and inorganic compounds and help to sequester a variety of metals. The mechanism by which Manganese (II) is oxidized to Manganese (IV) is a biologically catalyzed process. There are at least three different pathways by which Mn(II) can be bacterially oxidized to Mn(IV); the first in which states that Mn(II) can be oxidized to mixed Mn(III, IV), and Mn(IV) oxides and oxyhydroxides. The second of these pathways is that Mn(II) can be directly oxidized to Mn(IV) and the last of these pathways is that Mn(II) follows an enzymatic bond with a Mn(III) intermediate in which Mn(II) oxidizes to Mn(III) and then to Mn(IV). The pathways of focus for this research are the latter two pathways.

As the fast development of the electronic portable devices and drastic fading of fossil energy sources. The need for portable secondary energy sources is increasingly urgent. As a result, lithium ion batteries are being investigated intensely to meet the performance requirements. Among various electrode materials, the most expensive and capacity limiting component is the positive materials. Based on this, researches have been mostly focused on the development of novel cathode materials with high capacity and energy density and the lithium transition metal orthosilicates have been identified as possible high performance cathodes. Here in, we report the synthesis of a kind of lithium transition metal orthosilicates electrode lithium manganese silicate. Lithium manganese silicate has the advantage of high theoretical capacity, low cost raw material and safety. In this thesis, lithium manganese silicate are prepared using different silicon sources. The structure of silicon sources preferred are examined. Nonionic block copolymers surfactant, P123, is tried as carbon source and mophology directing agent. Lithium manganese silicate's performances are improved by adding P123.

Manganese (Mn) is an essential heavy metal that is naturally found in the environment. Daily intake through dietary sources provides the necessary amount required for several key physiological processes, including antioxidant defense, energy metabolism, immune function and others. However, overexposure from environmental sources can result in a condition known as manganism that features symptomatology similar to Parkinson's disease (PD). This disorder presents with debilitating motor and cognitive deficits that arise from a neurodegenerative process. In order to maintain a balance between its essentiality and neurotoxicity, several mechanisms exist to properly buffer cellular Mn levels. These include transporters involved in Mn uptake, and newly discovered Mn efflux mechanisms. This review will focus on current studies related to mechanisms underlying Mn import and export, primarily the Mn transporters, and their function and roles in Mn-induced neurotoxicity. Though and essential metal, overexposure to manganese may result in neurodegenerative disease analogous to Parkinson's disease. Manganese homeostasis is tightly regulated by transporters, including transmembrane importers (divalent metal transporter 1, transferrin and its receptor, zinc transporters ZIP8 and Zip14, dopamine transporter, calcium channels, choline transporters and citrate transporters) and exporters (ferroportin and SLC30A10), as well as the intracellular trafficking proteins (SPCA1 and ATP12A2). A manganese-specific sensor, GPP130, has been identified, which affords means for monitoring intracellular levels of this metal. PMID:25982296

Manganese is one of the most abundant metal in natural environments and serves as an essential microelement for all living systems. However, the enrichment of soil with manganese resulting from industrial inputs may threaten terrestrial ecosystems. Several studies have demonstrated harmful effects of manganese exposure by cutaneous contact and/or by soil ingestion to a wide range of soil invertebrates. The link between soil manganese and land snails has never been made although these invertebrates routinely come in contact with the upper soil horizons through cutaneous contact, egg-laying, and feeding activities in soil. Therefore, we have investigated the direct transfer of manganese from soils to snails and assessed its toxicity at background concentrations in the soil. Juvenile Cantareus aspersus snails were caged under semi-field conditions and exposed first, for a period of 30 days, to a series of soil manganese concentrations, and then, for a second period of 30 days, to soils with higher manganese concentrations. Manganese levels were measured in the snail hepatopancreas, foot, and shell. The snail survival and shell growth were used to assess the lethal and sublethal effects of manganese exposure. The transfer of manganese from soil to snails occurred independently of food ingestion, but had no consistent effect on either the snail survival or shell growth. The hepatopancreas was the best biomarker of manganese exposure, whereas the shell did not serve as a long-term sink for this metal. The kinetics of manganese retention in the hepatopancreas of snails previously exposed to manganese-spiked soils was significantly influenced by a new exposure event. The results of this study reveal the importance of land snails for manganese cycling in terrestrial biotopes and suggest that the direct transfer from soils to snails should be considered when precisely assessing the impact of anthropogenic Mn releases on soil ecosystems. PMID:24454856

We investigated the effect of silicide formation on ion-induced nanopatterning of silicon with various ultrathin metal coatings. Silicon substrates coated with 10 nm Ni, Fe, and Cu were irradiated with 200 eV argon ions at normal incidence. Real time grazing incidence small angle x-ray scattering (GISAXS) and x-ray fluorescence (XRF) were performed during the irradiation process and real time measurements revealed threshold conditions for nanopatterning of silicon at normal incidence irradiation. Three main stages of the nanopatterning process were identified. The real time GISAXS intensity of the correlated peaks in conjunction with XRF revealed that the nanostructures remain for a time period after the removal of the all the metal atoms from the sample depending on the binding energy of the metal silicides formed. Ex-situ XPS confirmed the removal of all metal impurities. In-situ XPS during the irradiation of Ni, Fe, and Cu coated silicon substrates at normal incidence demonstrated phase separation and the formation of different silicide phases that occur upon metal-silicon mixing. Silicide formation leads to nanostructure formation due the preferential erosion of the non-silicide regions and the weakening of the ion induced mass redistribution.

The iridium-silicon phase diagram on the silicon-rich side was investigated by means of X-ray powder diffraction, density, differential thermal analysis, metalography, microprobe analysis, and electrical resistivity. Attempts were made to prepare eight previously reported silicon-rich iridium silicide compounds by arc melting and Bridgman-like growth. However, microprobe analysis identified only four distinct compositions: IrSi, Ir3Si4, Ir3Si5 and IrSi sub about 3. The existence of Ir4Si5 could not be confirmed in this study, even though the crystal structure has been previously reported. Differential thermal analysis (DTA) in conjunction with X-ray powder diffraction confirm polymorphism in IrSi sub about 3, determined to have orthorhombic and monoclinic unit cells in the high and low temperature forms. A eutectic composition alloy of 83 +/- 1 atomic percent silicon was observed between IrSi sub about 3 and silicon. Ir3Si4 exhibits distinct metallic behavior while Ir3Si5 is semiconducting. Both and IrSi and IrSi sub about 3 exhibit nearly temperature independent electrical resistivities on the order of 5-10 x 10 exp -6 ohms-m.

Nd(5)CoSi(2) was obtained from the elements by arc-melting followed by annealing at 883 K. Its investigation by single-crystal x-ray and neutron powder diffraction shows that this ternary silicide crystallizes as Nd(5)Si(3) in a tetragonal structure deriving from the Cr(5)B(3)-type (I4/mcm space group; a = 7.7472(2) and c = 13.5981(5) Å as unit cell parameters). The structural refinements confirm the mixed occupancy on the 8h site between Si and Co atoms, as already observed for Gd(5)CoSi(2). Magnetization and specific heat measurements reveal a ferromagnetic behavior below T(C) = 55 K for Nd(5)CoSi(2). This magnetic ordering is further evidenced by neutron powder diffraction investigation revealing between 1.8 K and T(C) a canted ferromagnetic structure in the direction of the c-axis described by a propagation vector k = (0 0 0). At 1.8 K, the two Nd(3+) ions carry ordered magnetic moments equal respectively to 1.67(7) and 2.37(7) μ(B) for Nd1 and Nd2; these two moments exhibit a canting angle of θ = 4.3(6)°. This magnetic structure presents some similarities with that reported for Nd(5)Si(3). PMID:22392874

Given some transient power/cooling mismatch is a nuclear reactor and its inability to establish the necessary core cooling, energetic fuel-coolant interactions (FCI`s commonly called `vapor explosions`) could occur as a result of the core melting and coolant contact. Although a large number of studies have been done on energetic FCI`s, very few experiments have been performed with the actual fuel materials postulated to be produced in severe accidents. Because of the scarcity of well-characterized FCI data for uranium allows in noncommercial reactors (cermet and silicide fuels), we have conducted a series of experiments to provide a data base for the foregoing materials. An existing 1-D shock-tube facility was modified to handle depleted radioactive materials (U{sub 3}O{sub 8}-Al, and U{sub 3}Si{sub 2}-Al). Our objectives have been to determine the effects of the initial fuel composition and temperature and the driving pressure (triggering) on the explosion work output, dynamic pressures, transient temperatures, and the hydrogen production. Experimental results indicate limited energetics, mainly thermal interactions, for these fuel materials as compared to aluminum where more chemical reactions occur between the molten aluminum and water.

V-4Cr-4Ti vanadium alloy is a potential cladding material for sodium-cooled fast-neutron reactors (SFRs). However, its affinity for oxygen and the subsequent embrittlement that oxygen induces causes a need for an oxygen diffusion barrier, which can be obtained by manufacturing a multi-layered silicide coating. The present work aims to evaluate the effects of thermal cycling (using a cyclic oxidation device) and tensile and compressive stresses (using the three-point flexure test) on the coated alloy system. Tests were performed in air up to 1100 °C, which is 200 °C higher than the accidental temperature for SFR applications. The results showed that the VSi2 coating was able to protect the vanadium substrate from oxidation for more than 400 1-h cycles between 1100 °C and room temperature. The severe bending applied to the coated alloy at 950 °C using a load of 75 MPa did not lead to specimen breakage. It can be suggested that the VSi2 coating has mechanical properties compatible with the V-4Cr-4Ti alloy for SFR applications.

Aluminum silicide microparticles with oxidized rough surfaces were formed on Si substrates through a spontaneous granulation process of Al films. This microparticle formation was caused by interdiffusion of Al and Si atoms at hypoeutectic temperatures of Al-Si systems, which was driven by compressive stress stored in Al films. The size, density, and the composition of the microparticles could be controlled by adjusting the annealing temperature, time, and the film thickness. High-density microparticles of a size around 10 μm and with an atomic ratio of Si/Al of approximately 0.8 were obtained when a 90-nm-thick Al film on Si substrate was annealed for 9 h at 550°C. The microparticle formation resulted in a rapid increase of the sheet resistance, which is a consequence of substantial consumption of Al film. This simple route to size- and composition-controllable microparticle formation may lay a foundation stone for the thermoelectric study on Al-Si alloy-based heterogeneous systems. PMID:24994964

The JMTR was fully converted to LEU silicide (U{sub 3}Si{sub 2}) fuel with cadmium wires as burnable absorber in January, 1994. The reduced enrichment program for the JMTR was initiated in 1979, and the conversion to MEU (enrichment ; 45%) aluminide fuel was carried out in 1986 as the first step of the program. The final goal of the program was terminated by the present LEU conversion. This paper describes the results of core physics measurement through the conversion phase from MEU fuel core to LEU fuel core. Measured excess reactivities of the LEU fuel cores are mostly in good agreement with predicted values. Reactivity effect and burnup of cadmium wires, therefore, were proved to be well predicted. Control rod worth in the LEU fuel core is mostly less than that in the MEU fuel core. Shutdown margin was verified to be within the safety limit. There is no significant difference in temperature coefficient of reactivity between the MEU and LEU fuel cores. These results verified that the JMTR was successfully and safely converted to LEU fuel. Extension of the operating cycle period was achieved and reduction of spend fuel elements is expected by using the fuel with high uranium density.

Japan Research Reactor No.4 (JRR-4) is a light water moderated and cooled, 93% enriched uranium ETR-type fuel used and swimming pool type reactor with thermal output of 3.5MW. Since the first criticality was achieved on January 28, 1965, JRR-4 has been used for shielding experiments, radioisotope production, neutron activation analyses, training for reactor engineers and so on for about 30 years. Within the framework of the RERTR Program, the works for conversion to LEU fuel are now under way, and neutronic and thermal-hydraulic calculations emphasizing on safety and performance aspects are being carried out. The design and evaluation for the core conversion are based on the Guides for Safety Design and Evaluation of research and testing reactor facilities in Japan. These results show that the JRR-4 will be able to convert to use LEU fuel without any major design change of core and size of fuel element. LEU silicide fuel (19.75%) will be used and maximum neutron flux in irradiation hole would be slightly decreased from present neutron flux value of 7x10{sup 13}(n/cm{sup 2}/s). The conversion works are scheduled to complete in 1998, including with upgrade of the reactor building and utilization facilities.

We report experiments on surface nanopatterning of Si targets which are irradiated with 2-keV Ar+ ions impinging at near-glancing incidence, under concurrent codeposition of Au impurities simultaneously extracted from a gold target by the same ion beam. Previous recent experiments by a number of groups suggest that silicide formation is a prerequisite for pattern formation in the presence of metallic impurities. In spite of the fact that Au is known not to form stable compounds with the Si atoms, ripples nonetheless emerge in our experiments with nanometric wavelengths and small amplitudes, and with an orientation that changes with distance to the Au source. We provide results of sample analysis through Auger electron and energy-dispersive x-ray spectroscopies for their space-resolved chemical composition, and through atomic force, scanning transmission electron, and high-resolution transmission microscopies for their morphological properties. We discuss these findings in the light of current continuum models for this class of systems. The composition of and the dynamics within the near-surface amorphized layer that ensues is expected to play a relevant role to account for the unexpected formation of these surface structures.

Based on first-principles calculations and an effective Hamiltonian analysis, we systematically investigate the electronic and topological properties of alkaline-earth compounds A X2 (A =Ca , Sr, Ba; X =Si , Ge, Sn). Taking BaSn2 as an example, we find that when spin-orbit coupling is ignored, these materials are three-dimensional topological nodal-line semimetals characterized by a snakelike nodal loop in three-dimensional momentum space. Drumheadlike surface states emerge either inside or outside the loop circle on the (001) surface depending on surface termination, while complicated double-drumhead-like surface states appear on the (010) surface. When spin-orbit coupling is included, the nodal line is gapped and the system becomes a topological insulator with Z2 topological invariants (1;001). Since spin-orbit coupling effects are weak in light elements, the nodal-line semimetal phase is expected to be achievable in some alkaline-earth germanides and silicides.

High quality epitaxial Co and Fe silicides have been grown by molecular beam epitaxy on Si(111) and Si(001) substrates with film thicknesses ranging between 25 and 8400 A. We used Rutherford backscattering spectrometry channeling techniques to measure the lattice distortion as a function of film thickness. The critical thickness h(sub c) corresponding to the film thickness at which strain relieving dislocations begin to appear was determined for CoSi2 on Si(111) and Si(001) as well as for Si on CoSi2(111). For CoSi2 on Si(001), a larger critical thickness was obtained on Si(111), where h(sub c) is about 45A. Epitaxial Si on CoSi2(111) was found to be under a compressive strain up to thicknesses of about 350 a depending on substrate misorientation. Strain measurements were also performed on epitaxially stabilized Co and Fe monosilicides with the CsCl structure. Channeling measurements on thick epitaxial films of bcc-Fe, Fe3Si, FeSi, and Fe0.5Si were used to determine the crystalline quality. Excellent channeling minimum yields of 4.0% were found for bcc-Fe/Si(111). The results are compared with structural information obtained from x-ray diffraction and Brillouin scattering spectroscopy.

The interplay of manganese and iron homeostasis and oxidative stress in Escherichia coli can give important insights into survival of bacteria in the phagosome and under differing iron or manganese bioavailabilities. Here, we characterized a mutant strain devoid of all know iron/manganese-uptake systems relevant for growth in defined medium. Based on these results an exit strategy enabling the cell to cope with iron depletion and use of manganese as an alternative for iron could be shown. Such a strategy would also explain why E. coli harbors some iron- or manganese-dependent iso-enzymes such as superoxide dismutases or ribonucleotide reductases. The benefits for gaining a means for survival would be bought with the cost of less efficient metabolism as indicated in our experiments by lower cell densities with manganese than with iron. In addition, this strain was extremely sensitive to the metalloid gallium but this gallium toxicity can be alleviated by low concentrations of manganese. PMID:27003826

Manganese germanate nanorods have been synthesized by a simple route using germanium dioxide and manganese acetate as the source materials. X-ray diffraction observation shows that the nanorods are composed of orthorhombic and monoclinic manganese germanate phases. Scanning electron microscopy and transmission electron microscopy observations display that the manganese germanate nanorods have flat tips with the length of longer than 10 micrometers and diameter of 60-350 nm, respectively. The role of the growth conditions on the formation of the manganese germanate nanorods shows that the proper selection and combination of the growth conditions are the key factor for controlling the formation of the manganese germanate nanorods. The photoluminescence spectrum of the manganese germanate nanorods exhibits four fluorescence emission peaks centered at 422 nm, 472 nm, 487 nm and 530 nm showing the application potential for the optical devices. - Research Highlights: {yields} Manganese germanate nanorods have been synthesized by simple hydrothermal process. {yields} The formation of manganese germanate nanorods can be controlled by growth conditions. {yields} Manganese germanate nanorods exhibit good PL emission ability for optical device.

Channel stress induced by NiPt-silicide films in metal-oxide-semiconductor field-effect transistors (MOSFETs) was demonstrated using UV-Raman spectroscopy, and its generation mechanism was revealed. It was possible to accurately measure the channel stress with the Raman test structure. The channel stress depends on the source/drain doping type and the second silicide annealing method. In order to discuss the channel stress generation mechanism, NiPt-silicide microstructure analyses were performed using X-ray diffraction analysis and scanning transmission electron microscopy. The channel stress generation mechanism can be elucidated by the following two factors: the change in the NiSi lattice spacing, which depends on the annealing temperature, and the NiSi crystal orientation. The analyses of these factors are important for controlling channel stress in stress engineering for high-performance transistors.

Manganese oxides are considered as promising cathodes for rechargeable batteries due to their low cost and low toxicity as well as the abundant natural resources. In this dissertation, manganese oxides have been investigated as cathodes for both rechargeable lithium and alkaline batteries. Nanostructured lithium manganese oxides designed for rechargeable lithium cells have been synthesized by reducing lithium permanganate with methanol or hydrogen in various solvents followed by firing at moderate temperatures. The samples have been characterized by wet-chemical analyses, thermal methods, spectroscopic methods, and electron microscopy. It has been found that chemical residues in the oxides such as carboxylates and hydroxyl groups, which could be controlled by varying the reaction medium, reducing agents, and additives, make a significant influence on the electrochemical properties. The Li/Mn ratio in the material has also been found to be a critical factor in determining the rechargeability of the cathodes. The optimized samples exhibit a high capacity of close to 300 mAh/g with good cyclability and charge efficiency. The high capacity with a lower discharge voltage may make these nanostructured oxides particularly attractive for lithium polymer batteries. The research on the manganese oxide cathodes for alkaline batteries is focused on an analysis of the reaction products generated during the charge/discharge processes or by some designed chemical reactions mimicking the electrochemical processes. The factors influencing the formation of Mn3O4 in the two-electron redox process of delta-MnO2 have been studied with linear sweep voltammetry combined with X-ray diffraction. The presence of bismuth, the discharge rate, and the microstructure of the electrodes are found to affect the formation of Mn3O4, which is known to be electrochemically inactive. A faster voltage sweep and a more intimate mixing of the manganese oxide and carbon in the cathode are found to suppress

In this study, a method for preparing pure manganese sulfate from low-grade ores with a granule mean size of 0.47 mm by direct acid leaching was developed. The effects of the types of leaching agents, sulfuric acid concentration, reaction temperature, and agitation rate on the leaching efficiency of manganese were investigated. We observed that sulfuric acid used as a leaching agent provides a similar leaching efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sulfuric acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respectively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent activation energy of 12.28 kJ·mol-1. The purification conditions of the leaching solution were also discussed. The results show that manganese dioxide is a suitable oxidant of ferrous ions and sodium dimethyldithiocarbamate is an effective precipitant of heavy metals. Finally, through chemical analysis and X-ray diffraction analysis, the obtained product was determined to contain 98% of MnSO4·H2O.

Spinel-structured LiMn 2 O 4 (LMO) is a desirable cathode material for Li-ion batteries due to its low cost, abundance, and high power capability. However, LMO suffers from limited cycle life that is triggered by manganese dissolution into the electrolyte during electrochemical cycling. Here, it is shown that single-layer graphene coatings suppress manganese dissolution, thus enhancing the performance and lifetime of LMO cathodes. Relative to lithium cells with uncoated LMO cathodes, cells with graphene-coated LMO cathodes provide improved capacity retention with enhanced cycling stability. X-ray photoelectron spectroscopy reveals that graphene coatings inhibit manganese depletion from the LMO surface. Additionally, transmission electron microscopy demonstrates that a stable solid electrolyte interphase is formed on graphene, which screens the LMO from direct contact with the electrolyte. Density functional theory calculations provide two mechanisms for the role of graphene in the suppression of manganese dissolution. First, common defects in single-layer graphene are found to allow the transport of lithium while concurrently acting as barriers for manganese diffusion. Second, graphene can chemically interact with Mn 3+ at the LMO electrode surface, promoting an oxidation state change to Mn 4+ , which suppresses dissolution.

In this paper we investigate the two manganese pnictides BaMn2As2 and LaMnAsO, using fully charge self-consistent density functional plus dynamical mean-field theory calculations. These systems have a nominally half-filled d shell, and as a consequence, electronic correlations are strong, placing these compounds at the verge of a metal-insulator transition. Although their crystal structure is composed of similar building blocks, our analysis shows that the two materials exhibit a very different effective dimensionality, LaMnAsO being a quasi-two-dimensional material in contrast to the much more three-dimensional BaMn2As2 . We demonstrate that the experimentally observed differences in the Néel temperature, the band gap, and the optical properties of the manganese compounds under consideration can be traced back to exactly this effective dimensionality. Our calculations show excellent agreement with measured optical spectra.

Graded levels of manganese were supplemented to a semi-purified diet containing 45% crude protein, to provide six levels of manganese (i. e. containing 5, 25, 50, 70, 140 and 210×10-6, respectively) for two experiments with these experimental diets. The initial weight of shrimp used in the 35 day experiment I was 0.30±0.04 g, and that in the 70 day Experiment II was more than one gram. The results showed that optimum content in the semi-purified diet for the more than 1 gram shrimp ranged from 70 ×10-6, to 140×10-6, but supplementation of Mn was not necessary for the small shrimp.

The catalytic oxidation of water to molecular oxygen is a key process for the production of solar fuels. Inspired by the biological manganese-based active site for this reaction in the enzyme Photosystem II, researchers have made impressive progress in the last decades regarding the development of synthetic manganese catalysts for water oxidation. For this, it has been especially fruitful to explore the many different types of known manganese oxides MnOx. This chapter first offers an overview of the structural, thermodynamic, and mechanistic aspects of water-oxidation catalysis by MnOx. The different test systems used for catalytic studies are then presented together with general reactivity trends. As a result, it has been possible to identify layered, mixed Mn (III/IV)-oxides as an especially promising class of bio-inspired catalysts and an attempt is made to give structure-based reasons for the good performances of these materials. In the outlook, the challenges of catalyst screenings (and hence the identification of a "best MnOx catalyst") are discussed. There is a great variety of reaction conditions which might be relevant for the application of manganese oxide catalysts in technological solar fuel-producing devices, and thus catalyst improvements are currently still addressing a very large parameter space. Nonetheless, detailed knowledge about the biological catalyst and a solid experimental basis concerning the syntheses and water-oxidation reactivities of MnOx materials have been established in the last decade and thus this research field is well positioned to make important contributions to solar fuel research in the future. PMID:25980320

Molybdenum based refractory alloys are potential candidate materials for structural applications in high temperature compact nuclear reactors and fusion reactors. However, these alloys being highly susceptible to oxidation in air or oxygen at elevated temperature, undergoes severe losses from highly volatile molybdenum trioxide species. Present investigation, therefore, examines the feasibility of development of silicide type of coating over molybdenum base TZM alloy shape (Mo > 99 wt.%) using pack cementation coating technique. TZM alloy was synthesized in this laboratory from oxide intermediates of MoO 2, TiO 2 and ZrO 2 in presence of requisite amount of carbon, by alumino-thermic reduction smelting technique. The arc melted and homogenized samples of TZM alloy substrate was then embedded in the chosen and intimately mixed pack composition consisting of inert matrix (Al 2O 3), coating powder (Si) and activator (NH 4Cl) taken in the judicious proportion. The sealed charge packs contained in an alumina crucible were heated at temperatures of 1000 °C for 8-16 h heating cycle to develop the coating. The coating phase was confirmed to be of made of MoSi 2 by XRD analysis. The morphology of the coating was studied by SEM characterization. It had revealed that the coating was diffusion bonded where Si from coating diffused inward and Mo from TZM substrate diffused outward to form the coating. The coating was found to be resistant to oxidation when tested in air up to 1200 °C. A maximum 100 μm of coating thickness was achieved on each side of the substrate.

Transition metal silicides are being considered for future engine turbine components at temperatures up to 1600ºC. Although significant improvement in high temperature strength, room temperature fracture toughness has been realized in the past decade, further improvement in oxidation resistance is needed. Oxidation mechanism of Ti5Si3-based alloys was investigated. Oxidation behavior of Ti5Si3-based alloy strongly depends on the atmosphere. Presence of Nitrogen alters the oxidation behavior of Ti5Si3 by nucleation and growth of nitride subscale. Ti5Si3.2 and Ti5Si3C0.5 alloys exhibited an excellent oxidation resistance in nitrogen bearing atmosphere due to limited dissolution of nitrogen and increased Si/Ti activity ratio. MoSi2 coating developed by pack cementation to protect Mo-based Mo-Si-B composites was found to be effective up to 1500ºC. Shifting coating composition to T1+T2+Mo3Si region showed the possibility to extend the coating lifetime above 1500ºC by more than ten times via formation of slow growing Mo3Si or T2 interlayer without sacrificing the oxidation resistance of the coating. The phase equilibria in the Nb-rich portion of Nb-B system has been evaluated experimentally using metallographic analysis and differential thermal analyzer (DTA). It was shown that Nbss (solid solution) and NbB are the only two primary phases in the 0-40 at.% B composition range, and the eutectic reaction L ↔ Nbss + NbB was determined to occur at 2104+/-5°C by DTA.

Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves and methods of making the same are disclosed. A method for forming nanowires includes hydrothermally treating a chemical precursor composition in a hydrothermal treating solvent to form the nanowires, wherein the chemical precursor composition comprises a source of manganese cations and a source of counter cations, and wherein the nanowires comprise ordered porous manganese oxide-based octahedral molecular sieves.

This study provides a physicochemical assessment of manganese deposits on brass and lead components from two fully operational drinking water distributions systems. One of the systems was maintained with chlorine; the other, with secondary chloramine disinfection. Synchrotron-based in-situ micro X-ray adsorption near edge structure was used to assess the mineralogy. In-situ micro X-ray fluorescence mapping was used to demonstrate the spatial relationships between manganese and potentially toxic adsorbed metal ions. The Mn deposits ranged in thickness from 0.01 to 400 μm. They were composed primarily of Mn oxides/oxhydroxides, birnessite (Mn(3+) and Mn(4+)) and hollandite (Mn(2+) and Mn(4+)), and a Mn silicate, braunite (Mn(2+) and Mn(4+)), in varying proportions. Iron, chromium, and strontium, in addition to the alloying elements lead and copper, were co-located within manganese deposits. With the exception of iron, all are related to specific health issues and are of concern to the U.S. Environmental Protection Agency (U.S. EPA). The specific properties of Mn deposits, i.e., adsorption of metals ions, oxidation of metal ions and resuspension are discussed with respect to their influence on drinking water quality. PMID:26409148

The deposition of manganese in a water distribution system with manganese-related "dirty water" problems was studied over a 1-year period. Four monitoring laboratories with Robbins biofilm sampling devices fitted to the water mains were used to correlate the relationship among manganese deposition, the level of manganese in the water, and the chlorination conditions. Manganese deposition occurred by both chemical and microbial processes. Chemical deposition occurred when Mn(II) not removed during water treatment penetrated the filters and entered the distribution system, where it was oxidized by chlorine and chlorine dioxide used for disinfection. Microbial deposition occurred in areas with insufficient chlorination to control the growth of manganese-depositing biofilm. At 0.05 mg of Mn(II) per liter, the chemical deposition rate was much greater than microbial deposition. Significant deposition occurred at 0.03 mg of manganese per liter, and dirty water complaints were not eliminated until manganese levels were continuously less than 0.02 mg/liter and chlorination levels were greater than 0.2 mg/liter. A guideline level of 0.01 mg of manganese per liter is recommended. Images PMID:2317040

Paramagnetic manganese (II) can be employed as a calcium surrogate to sensitize magnetic resonance microscopy (MRM) to the processing of calcium during bone formation. At high doses, osteoblasts can take up sufficient quantities of manganese, resulting in marked changes in water proton T1, T2 and magnetization transfer ratio values compared to those for untreated cells. Accordingly, inductively coupled plasma mass spectrometry (ICP-MS) results confirm that the manganese content of treated cell pellets was 10-fold higher than that for untreated cell pellets. To establish that manganese is processed like calcium and deposited as bone, calvaria from the skull of embryonic chicks were grown in culture medium supplemented with 1 mM MnCl2 and 3 mM CaCl2. A banding pattern of high and low T2 values, consistent with mineral deposits with high and low levels of manganese, was observed radiating from the calvarial ridge. The results of ICP-MS studies confirm that manganese-treated calvaria take up increasing amounts of manganese with time in culture. Finally, elemental mapping studies with electron probe microanalysis confirmed local variations in the manganese content of bone newly deposited on the calvarial surface. This is the first reported use of manganese-enhanced MRM to study the process whereby calcium is taken up by osteoblasts cells and deposited as bone. ?? 2007 Elsevier Inc. All rights reserved.

The ICRP is updating its recommendations regarding occupational exposure to radionuclides including the biokinetic models used to derive dose coefficients and assess bioassay data for internally deposited radionuclides. This report reviews biokinetic data for manganese and proposes a biokinetic model for systemic manganese consistent with the current database. The model provides a more detailed and biologically realistic description of the movement of absorbed manganese in the body than the model currently recommended by the International Commission on Radiological Protection (ICRP). The proposed model and current ICRP model yield broadly similar estimates of dose per unit activity of inhaled or ingested radio-manganese but differ substantially with regard to interpretation of bioassay data.

We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. PMID:25044528

Manganese regulates many enzymes and is essential for normal cell function. Chronic manganese intoxication has an insidious and progressive course terminating to atypical parkinsonism with little therapeutic efficacy. For subjects with chronic manganese exposure such as welders, manganese intoxication can be detected early based on the presence of hyperintensity in the globus pallidus on T(1)-weighted MRI and abnormally high urinary excretion of manganese with a chelating agent even in cases of normal serum/urine level of manganese. PMID:26873238

Manganese-enhanced MRI has recently become a valuable tool for the assessment of in vivo functional cerebral activity in animal models. As a result of the toxicity of manganese at higher dosages, fractionated application schemes have been proposed to reduce the toxic side effects by using lower concentrations per injection. Here, we present data on regional-specific manganese accumulation during a fractionated application scheme over 8 days of 30 mg/kg MnCl2 , as well as on the clearance of manganese chloride over the course of several weeks after the termination of the whole application protocol supplying an accumulative dose of 240 mg/kg MnCl2 . Our data show most rapid accumulation in the superior and inferior colliculi, amygdala, bed nucleus of the stria terminalis, cornu ammonis of the hippocampus and globus pallidus. The data suggest that no ceiling effects occur in any region using the proposed application protocol. Therefore, a comparison of basal neuronal activity differences in different animal groups based on locally specific manganese accumulation is possible using fractionated application. Half-life times of manganese clearance varied between 5 and 7 days, and were longest in the periaqueductal gray, amygdala and entorhinal cortex. As the hippocampal formation shows one of the highest T1 -weighted signal intensities after manganese application, and manganese-induced memory impairment has been suggested, we assessed hippocampus-dependent learning as well as possible manganese-induced atrophy of the hippocampal volume. No interference of manganese application on learning was detected after 4 days of Mn(2+) application or 2 weeks after the application protocol. In addition, no volumetric changes induced by manganese application were found for the hippocampus at any of the measured time points. For longitudinal measurements (i.e. repeated manganese applications), a minimum of at least 8 weeks should be considered using the proposed protocol to allow for

The remarkable aliphatic C-H hydroxylations catalyzed by the heme-containing enzyme, cytochrome P450, have attracted sustained attention for more than four decades. The effectiveness of P450 enzymes as highly selective biocatalysts for a wide range of oxygenation reactions of complex substrates has driven chemists to develop synthetic metalloporphyrin model compounds that mimic P450 reactivity. Among various known metalloporphyrins, manganese derivatives have received considerable attention since they have been shown to be versatile and powerful mediators for alkane hydroxylation and olefin epoxidation. Mechanistic studies have shown that the key intermediates of the manganese porphyrin-catalyzed oxygenation reactions include oxo- and dioxomanganese(V) species that transfer an oxygen atom to the substrate through a hydrogen abstraction/oxygen recombination pathway known as the oxygen rebound mechanism. Application of manganese porphyrins has been largely restricted to catalysis of oxygenation reactions until recently, however, due to ultrafast oxygen transfer rates. In this Account, we discuss recently developed carbon-halogen bond formation, including fluorination reactions catalyzed by manganese porphyrins and related salen species. We found that biphasic sodium hypochlorite/manganese porphyrin systems can efficiently and selectively convert even unactivated aliphatic C-H bonds to C-Cl bonds. An understanding of this novel reactivity derived from results obtained for the oxidation of the mechanistically diagnostic substrate and radical clock, norcarane. Significantly, the oxygen rebound rate in Mn-mediated hydroxylation is highly correlated with the nature of the trans-axial ligands bound to the manganese center (L-Mn(V)═O). Based on the ability of fluoride ion to decelerate the oxygen rebound step, we envisaged that a relatively long-lived substrate radical could be trapped by a Mn-F fluorine source, effecting carbon-fluorine bond formation. Indeed, this idea

Silicon nanowires grown using the vapor-liquid-solid method are promising candidates for nanoelectronics applications. The nanowires grow from an Au-Si catalyst during silicon chemical vapor deposition. In this paper, the effect of temperature, oxide at the interface and substrate orientation on the nucleation and growth kinetics during formation of nanogold silicide structures is explained using an oxide mediated liquid-solid growth mechanism. Using real time in situ high temperature transmission electron microscopy (with 40 ms time resolution), we show the formation of high aspect ratio ( approximately 15.0) aligned gold silicide nanorods in the presence of native oxide at the interface during in situ annealing of gold thin films on Si(110) substrates. Steps observed in the growth rate and real time electron diffraction show the existence of liquid Au-Si nano-alloy structures on the surface besides the un-reacted gold nanostructures. These results might enable us to engineer the growth of nanowires and similar structures with an Au-Si alloy as a catalyst. PMID:19843987

Silicon nanowires grown using the vapor-liquid-solid method are promising candidates for nanoelectronics applications. The nanowires grow from an Au-Si catalyst during silicon chemical vapor deposition. In this paper, the effect of temperature, oxide at the interface and substrate orientation on the nucleation and growth kinetics during formation of nanogold silicide structures is explained using an oxide mediated liquid-solid growth mechanism. Using real time in situ high temperature transmission electron microscopy (with 40 ms time resolution), we show the formation of high aspect ratio (≈15.0) aligned gold silicide nanorods in the presence of native oxide at the interface during in situ annealing of gold thin films on Si(110) substrates. Steps observed in the growth rate and real time electron diffraction show the existence of liquid Au-Si nano-alloy structures on the surface besides the un-reacted gold nanostructures. These results might enable us to engineer the growth of nanowires and similar structures with an Au-Si alloy as a catalyst.

A 50-nm thick polycrystalline Si film was fabricated by the crystallization of anamorphous Si film using silicide-enhanced rapid thermal annealing (SERTA). The amorphous Si film was deposited on a 5-nm thick polycrystalline Si seed layer containing nickel silicide precipitates in grain boundary areas. With the help of the silicide precipitates, the RTA temperature decreased from 730 to 680°C and the grain size of the crystallized polycrystalline Si film increased to 1.4 — 2.2 μm. Few defects were found within the grains and the Ni concentration in the polycrystalline film decreased to 1 × 1018 cm-3 due to the very-thin seed layer that contained nickel silicide precipitates. As a result, the field-effect hole mobility in the p-channel poly-Si thin film transistors (TFTs), fabricated employing the polycrystalline Si film, was as high as 169 cm2/V•s at a drain voltage of V D = -0.1 V; the subthreshold swing was as small as 0.24 V/decade. The minimum leakage current at V D= 5V was 1.5 × 10-10 A with very good diode characteristics. [Figure not available: see fulltext.

Work done during the final report period is presented. The main technical objective was to achieve epitaxial growth on silicon of two semiconducting silicides, ReSi2 and CrSi2. ReSi2 thin films were grown on (001) silicon wafers by vacuum evaporation of rhenium onto hot substrates in ultrahigh vacuum. The preferred epitaxial relationship was found to be ReSi2(100)/Si(001) with ReSi2(010) parallel to Si(110). The lattice matching consists of a common unit mesh of 120 A(sup 2) area, and a mismatch of 1.8 percent. Transmission electron microscopy revealed the existence of rotation twins corresponding to two distinct but equivalent azimuthal orientations of the common unit mesh. MeV He(+) backscattering spectrometry revealed a minimum channeling yield of 2 percent for an approximately 1,500 A thick film grown at 650 C. Although the lateral dimension of the twins is on the order of 100 A, there is a very high degree of alignment between the ReSi2(100) and the Si(001) planes. Highly oriented films of CrSi2 were grown on (111) silicon substrates, with the matching crystallographic faces being CrSi2(001)/Si(111). The reflection high-energy electron diffraction (RHEED) patterns of the films consist of sharp streaks, symmetrically arranged. The predominant azimuthal orientation of the films was determined to be CrSi2(210) parallel to Si(110). This highly desirable heteroepitaxial relationship has been obtained previously by others; it may be described with a common unit mesh of 51 A(sup 2) and mismatch of 0.3 percent. RHEED also revealed the presence of limited film regions of a competing azimuthal orientation, CrSi2(110) parallel to Si(110). A channeling effect for MeV He(+) ions was not found for this material. Potential commercial applications of this research may be found in silicon-integrated infrared detector arrays. Optical characterizations showed that semiconducting ReSi2 is a strong absorber of infrared radiation, with the adsorption constant increasing above 2 x

Dissimilatory manganese reduction dominates anaerobic carbon oxidation in marine sediments with high manganese oxide concentrations, but the microorganisms responsible for this process are largely unknown. In this study, the acetate-utilizing manganese-reducing microbiota in geographically well-separated, manganese oxide-rich sediments from Gullmar Fjord (Sweden), Skagerrak (Norway) and Ulleung Basin (Korea) were analyzed by 16S rRNA-stable isotope probing (SIP). Manganese reduction was the prevailing terminal electron-accepting process in anoxic incubations of surface sediments, and even the addition of acetate stimulated neither iron nor sulfate reduction. The three geographically distinct sediments harbored surprisingly similar communities of acetate-utilizing manganese-reducing bacteria: 16S rRNA of members of the genera Colwellia and Arcobacter and of novel genera within the Oceanospirillaceae and Alteromonadales were detected in heavy RNA-SIP fractions from these three sediments. Most probable number (MPN) analysis yielded up to 10(6) acetate-utilizing manganese-reducing cells cm(-3) in Gullmar Fjord sediment. A 16S rRNA gene clone library that was established from the highest MPN dilutions was dominated by sequences of Colwellia and Arcobacter species and members of the Oceanospirillaceae, supporting the obtained RNA-SIP results. In conclusion, these findings strongly suggest that (i) acetate-dependent manganese reduction in manganese oxide-rich sediments is catalyzed by members of taxa (Arcobacter, Colwellia and Oceanospirillaceae) previously not known to possess this physiological function, (ii) similar acetate-utilizing manganese reducers thrive in geographically distinct regions and (iii) the identified manganese reducers differ greatly from the extensively explored iron reducers in marine sediments. PMID:22572639

In media containing normal trace-element supplements, but not in manganese-deficient media, zygospores of a new species of Chlamydomonas (isolated from soil) become encrusted with a dark brown mineral coating. Staining with benzidine indicates that the encrustation is rich in manganese. This has been confirmed by x-ray analysis in combination with a scanning electron microscope. PMID:17798436

This indicator presents trends in ambient concentrations of manganese in EPA Region 5 from 2000 to 2009. This information shows how concentrations of manganese, a hazardous air pollutant that can harm human health in exposed populations, have changed in the last 10 years in a ...

... orders on imports of electrolytic manganese dioxide from Greece and Japan (54 FR 15243). The Commission..., including the text of subpart F of part 207, are published at 63 FR 30599, June 5, 1998, and may be... COMMISSION Electrolytic Manganese Dioxide From Greece and Japan AGENCY: United States International...

Analyses of the bulk oxidation state of marine manganese nodules indicates that more than 98% of the Mn in deep ocean nodules is present as Mn(IV). The samples were collected from three quite different areas: the hemipelagic environment of the Guatemala Basin, the pelagic area of the North Pacific, and seamounts in the central Pacific. Results of the study suggest that todorokite in marine nodules is fully oxidized and has the following stoichiometry: (K, Na, Ca, Ba).33(Mg, Cu, Ni).76Mn5O22(H2O)3.2. ?? 1984.

We report the parameterization of AM1* for the elements manganese and iron. The basis sets for both metals contain one set each of s-, p- and d-orbitals. AM1* parameters are now available for H, C, N, O and F (which use the original AM1 parameters), Al, Si, P, S, Cl, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Br, Zr, Mo, I and Au. The performance and typical errors of AM1* are discussed for Mn and Fe, and are compared with available NDDO Hamiltonians. PMID:19937261

A manganese-oxidizing bacteria (QJX-1) was isolated from the soil of a manganese mine. It was identified as Pseudomonas sp. QJX-1 by 16S rDNA sequencing. Experimental results showed that the Pseudomonas sp. QJX-1 has a multi-copper oxidase gene CumA, which is an essential component for manganese oxidation by Pseudomonas sp. Under the condition of low initial inoculum level (D600, 0.020), 5.05 mg x L(-1 Mn2+ could be oxidized by QJX-1 within 48 h with a conversion rate of as high as 99.4%. In comparison with the eutrophic conditions, the oligotrophic condition dramatically increased the biological manganese oxidation rate. Biofilm formation by employing the quartz sand could further improve the oxidation rate of Mn2+. Based on these results, it is speculated that biological manganese oxidation in underground water treatment is comparatively high. PMID:24812972

Manganese sequestering by nearly simultaneous additions of sodium silicate and sodium hypochlorite was studied in laboratory-prepared waters. Under conditions of near-neutral pH and 150-250 mg/liter of alkalinity as CaCO{sub 3}, 1-2 mg manganese/liter could be sequestered for up to one day. Less effective manganese treatability was found at pH 8 than at pH 7. Additionally, at pH 7 the best results were obtained when neither silicate nor hypochlorite was added because of the slow manganese oxidation rate by oxygen alone. Aging of diluted stock silicate solutions prior to dosing also resulted in poor treatment; the presence of background silica increased the treatment effectiveness only slightly. Overall, manganese was less treatable by this method than iron under the same treatment conditions.

The report follows the flow of manganese through its metallurgical and chemical applications and highlights areas where significant losses occur owing to downgrading, export, or disposal. The study indicates that materials containing 695,000 short tons (st) of manganese were consumed domestically in 1990. Scrap recovery specifically for manganese recycling was insignificant. However, considerable manganese was recycled through processing operations as a minor component of ferrous and nonferrous scrap and steel slag. The major loss category is manganese lost in steel processing, 323,156 st or 46 pct of the 1990 apparent consumption. Most of this loss reports to steelmaking slags. Recovery from slags is technically feasible, but is not economically feasible.

We studied the response of gypsy moth (Lymantria dispar (Linnaeus) (Lepidoptera: Lymantriidae)) to the content of manganese in food in the laboratory breeding of caterpillars. The food of the caterpillars {Betula pendula Roth (Fagales: Betulaceae) leaves} was contaminated by dipping in the solution of MnCl2 · 4H2O with manganese concentrations of 0, 0.5, 5 and 10 mg ml(-1), by which differentiated manganese contents (307; 632; 4,087 and 8,124 mg kg(-1)) were reached. Parameters recorded during the rearing were as follows: effect of manganese on food consumption, mortality and length of the development of caterpillars, pupation and hatching of imagoes. At the same time, manganese concentrations were determined in the offered and unconsumed food, excrements, and exuviae of the caterpillars, pupal cases and imagoes by using the AAS method. As compared with the control, high manganese contents in the food of gypsy moth caterpillars affected the process of development particularly by increased mortality of the first instar caterpillars (8 % mortality for caterpillars with no Mn contamination (T0) and 62 % mortality for subjects with the highest contamination by manganese (T3)), by prolonged development of the first-third instar (18.7 days (T0) and 27.8 days (T3)) and by increased food consumption of the first-third instar {0.185 g of leaf dry matter (T0) and 0.483 g of leaf dry matter (T3)}. The main defence strategy of the caterpillars to prevent contamination by the increased manganese content in food is the translocation of manganese into frass and exuviae castoff in the process of ecdysis. In the process of development, the content of manganese was reduced by excretion in imagoes to 0.5 % of the intake level even at its maximum inputs in food. PMID:25028315

Risk assessments of manganese by inhalation or oral routes of exposure typically acknowledge the duality of manganese as an essential element at low doses and a toxic metal at high doses. Previously, however, risk assessors were unable to describe manganese pharmacokinetics quantitatively across dose levels and routes of exposure, to account for mass balance, and to incorporate this information into a quantitative risk assessment. In addition, the prior risk assessment of inhaled manganese conducted by the U.S. Environmental Protection Agency (EPA) identified a number of specific factors that contributed to uncertainty in the risk assessment. In response to a petition regarding the use of a fuel additive containing manganese, methylcyclopentadienyl manganese tricarbonyl (MMT), the U.S. EPA developed a test rule under the U.S. Clean Air Act that required, among other things, the generation of pharmacokinetic information. This information was intended not only to aid in the design of health outcome studies, but also to help address uncertainties in the risk assessment of manganese. To date, the work conducted in response to the test rule has yielded substantial pharmacokinetic data. This information will enable the generation of physiologically based pharmacokinetic (PBPK) models capable of making quantitative predictions of tissue manganese concentrations following inhalation and oral exposure, across dose levels, and accounting for factors such as duration of exposure, different species of manganese, and changes of age, gender, and reproductive status. The work accomplished in response to the test rule, in combination with other scientific evidence, will enable future manganese risk assessments to consider tissue dosimetry more comprehensively than was previously possible. PMID:20077286

The experiment investigated effects of high quantities of manganese and route of administration (diet versus capsule-dosed) on feed intake and blood characteristics in sheep. Twenty-four Florida native or Florida native by St. Croix crossbred wethers, 47 kg initially, were assigned randomly to eight treatments including basal diet supplemented with 0, 3000, 6000, or 9000 ppm manganese as a reagent grade manganese monoxide or basal diet plus gelatin capsules containing the equivalent of 0, 3000, 6000, or 9000 ppm manganese based on intake of the previous day. Three sheep per treatment were provided feed and tap water for ad libitum intake. Sheep were fed basal diet for 7 days followed by a 21-day experimental period, then placed back on the basal diet for 7 days. Average daily feed intake was reduced by increasing supplemental manganese, regardless of route. Animals dosed by capsule consumed less feed than those administered manganese in the diet. Serum manganese increased as manganese supplementation increased, but route of administration had no effect.

X-ray absorption spectra at the Manganese K-edge are presented for spinach chloroplasts, and chloroplasts which have been Tris-treated and hence unable to evolve oxygen. A significant change in the electronic environment of manganese is observed and is attributed to the release of manganese from the thylakoid membranes with a concomitant change in oxidation state. A correlation of the K-edge energy, defined as the energy at the first inflection point, with coordination charge has been established for a number of manganese compounds of known structure and oxidation state. Comparison of the manganese K-edge energies of the chloroplast samples with the reference compounds places the average oxidation state of the chloroplasts between +2 and +3. Using the edge spectra for Tris-treated membranes which were osmotically shocked to remove the released manganese, difference edge spectra were synthesized to approximate the active pool of manganese. Coordination charge predictions for this fraction are consistent with an average resting oxidation state higher than +2. The shape at the edge is also indicative of heterogeneity of the manganese site, of low symmetry, or both.

As biological manganese (Mn) removal becomes a more popular water treatment technology, there is still a large gap in understanding the key mechanisms and range of operational characteristics. This research aimed to expand on previous bench-scale experiments by directly comparing small filtration columns inoculated with indigenous biofilms from a Mn filtration plant and filtration columns inoculated with a liquid suspension of Leptothrix discophora SP-6. Batch tests found that in the absence of manganese oxidizing bacteria Mn was not removed by air alone, whereas a mixed population and Leptothrix strain achieved greater than 90% removal of Mn. The bench-scale biofiltration experiments found that biological filters can be inoculated with a pure culture of L. discophora SP-6 and achieve a similar removal of indigenous biofilm. While Mn oxidizing bacteria (MOB) seem to be necessary for the auto-catalytic nature of these biological filters, Mn removal is achieved with a combination of adsorption to Mn oxides and biological oxidation. Additionally, it was demonstrated that biological Mn removal is possible over a broader "field of activity" (e.g., Mn removal occurred at a pH level as low as 6.5) than has previously been reported. The ability of this treatment technology to work over a broader range of influent conditions allows for more communities to consider biological treatment as an option to remove Mn from their drinking water. PMID:18809196

High-dispersion plates secured with the Coudé spectrograph of the Lick 120 inch telescope have been used to analyze the peculiar A star π1 Bootis. Spectral-energy distribution measurements are combined with line-intensity data for iron and manganese in two stages of ionization to obtain a fit with model atmospheres for Teff = 13,000°K and log g = 4. The influence of adopted T and g on the derived abundances is discussed. Although C, O, Mg, Si, Ti, Cr, and Fe appear to have nearly normal (i.e., solar) abundances, strontium appears to be enhanced in abundance by an order of magnitude, and scandium is about 50 times overabundant, while manganese and yttrium appear to be two orders of magnitude overabundant. If the identification of gallium is correct, this element is overabundant by a factor approaching 100,000; while if λ3983.90 is to be attributed to HgII, as Bidelman suggests, the overabundance of this element is many orders of magnitude. PMID:16578698

The use of manganese ions (Mn2+) as an MRI contrast agent was introduced over 20 years ago in studies of Mn2+ toxicity in anesthetized rats (1). Manganese-enhanced MRI (MEMRI) evolved in the late nineties when Koretsky and associates pioneered the use of MEMRI for brain activity measurements (2) as well as neuronal tract tracing (3). Currently, MEMRI has three primary applications in biological systems: (1) contrast enhancement for anatomical detail, (2) activity-dependent assessment and (3) tracing of neuronal connections or tract tracing. MEMRI relies upon the following three main properties of Mn2+: (1) it is a paramagnetic ion that shortens the spin lattice relaxation time constant (T1) of tissues, where it accumulates and hence functions as an excellent T1 contrast agent; (2) it is a calcium (Ca2+) analog that can enter excitable cells, such as neurons and cardiac cells via voltage-gated Ca2+ channels; and (3) once in the cells Mn2+ can be transported along axons by microtubule-dependent axonal transport and can also cross synapses trans-synaptically to neighboring neurons. This chapter will emphasize the methodological approaches towards the use of MEMRI in biological systems. PMID:21279601

Oxide melt solution calorimetry has been performed on iron manganese oxide spinels prepared at high temperature. The enthalpy of formation of (Mn{sub x}Fe{sub 1-x}){sub 3}O{sub 4} at 298K from the oxides, tetragonal Mn{sub 3}O{sub 4} (hausmannite) and cubic Fe{sub 3}O{sub 4} (magnetite), is negative from x=0 to x=0.67 and becomes slightly positive for 0.670.6) spinels of intermediate compositions. The enthalpies of formation are discussed in terms of three factors: oxidation-reduction relative to the end-members, cation distribution, and tetragonality. A combination of measured enthalpies and Gibbs free energies of formation in the literature provides entropies of mixing. {delta}S{sub mix}, consistent with a cation distribution in which all trivalent manganese is octahedral and all other ions are randomly distributed for x>0.5, but the entropy of mixing appears to be smaller than these predicted values for x<0.4.

Reaction of the amidinato-manganese(ii) bromide complex, [{(κ(2)-N,N'-Piso)Mn(μ-Br)}3(THF)2] (Piso = [(DipN)2CBu(t)](-), Dip = 2,6-diisopropylphenyl), with K[BHEt3] affords the first example of a structurally authenticated amidinato-manganese(ii) hydride complex, [{(N-,η(3)-arene-Piso)Mn(μ-H)2}2], via a process which involves a change in the amidinate coordination mode. Treatment of the bulkier precursor complex, [{(Piso'')Mn(μ-Br)}n] (Piso'' = [(Dip''N)2CBu(t)](-), Dip'' = C6H2Pr(i)2(CPh3)-2,6,4), with K[BHEt3] did not lead to an isolable manganese hydride complex, but its reaction with the magnesium(i) complex, [{((Mes)Nacnac)Mg}2] ((Mes)Nacnac = [(MesNCMe)2CH](-), Mes = mesityl), did. This reaction presumably proceeds via a reactive manganese(i) intermediate, which abstracts hydrogen from a reaction component to give [{(κ(2)-N,N'-Piso'')Mn(μ-H)}3]. A comparison of the reactivities of [{(N-,η(3)-arene-Piso)Mn(μ-H)2}2] and the isomorphous manganese(i) complex, [{(N-,η(3)-arene-Piso)Mn}2], toward CO, O2 and N2O was carried out. Reactions with the manganese(i) and manganese(ii) species gave identical results, namely the formation of the manganese(i) carbonyl complex, [(κ(2)-N,N'-Piso)Mn(CO)4] (reactions with CO), and the manganese(iii)-μ-oxo complex, [{(κ(2)-N,N'-Piso)Mn(μ-O)}2] (reactions with O2 and N2O). These results indicate that [{(N-,η(3)-arene-Piso)Mn(μ-H)2}2] can act as a "masked" source of an amidinato-manganese(i) fragment in synthetic transformations. PMID:26674008

The release of manganese into water from controlled-release formulations containing manganese EDTA or manganese lignosulfonate was studied. These fertilizers were obtained in the laboratory by adhering the source of manganese over urea pellets and by adding a coating. The materials used as adhesives and coatings were mixtures of rosins plus tricalcium phosphate. With regard to the chemical composition, these formulations conformed to national and international standards for commercial fertilizers. The rate of release of manganese was a function of both the source of manganese used and the coating thickness. Under the same conditions the release of manganese was greater for formulations with manganese EDTA than with manganese lignosulfonate. To predict the kinetic behaviors of the two series of formulations, mathematical equations were established. The manganese source plus rosin coatings improved the handling and storage characteristics of the commercial urea pellets. The study of the rosin coatings using scanning electron microscopy showed that they were compact and homogeneous. PMID:11312854

We have investigated the electronic structure, phonon modes and electron-phonon coupling to understand superconductivity in the ternary silicide NaAlSi with a layered diamond-like structure. Our electronic results, using the density functional theory within a generalized gradient approximation, indicate that the density of states at the Fermi level is mainly governed by Si p states. The largest contributions to the electron-phonon coupling parameter involve Si-related vibrations both in the x-y plane as well as along the z-axis in the x-z plane. Our results indicate that this material is an s-p electron superconductor with a medium level electron-phonon coupling parameter of 0.68. Using the Allen-Dynes modification of the McMillan formula we obtain the superconducting critical temperature of 6.98 K, in excellent agreement with experimentally determined value of 7 K.

Several Mousterian sites in France have yielded large numbers of small black blocs. The usual interpretation is that these ‘manganese oxides’ were collected for their colouring properties and used in body decoration, potentially for symbolic expression. Neanderthals habitually used fire and if they needed black material for decoration, soot and charcoal were readily available, whereas obtaining manganese oxides would have incurred considerably higher costs. Compositional analyses lead us to infer that late Neanderthals at Pech-de-l’Azé I were deliberately selecting manganese dioxide. Combustion experiments and thermo-gravimetric measurements demonstrate that manganese dioxide reduces wood’s auto-ignition temperature and substantially increases the rate of char combustion, leading us to conclude that the most beneficial use for manganese dioxide was in fire-making. With archaeological evidence for fire places and the conversion of the manganese dioxide to powder, we argue that Neanderthals at Pech-de-l’Azé I used manganese dioxide in fire-making and produced fire on demand. PMID:26922901

Carbonate minerals such as dolomite, kutnahorite or rhodochrosite are frequently, but not exclusively generated by microbial processes. In recent anoxic sediments, Mn(II)carbonate minerals (e.g. rhodochrosite, kutnahorite) derive mainly from the reduction of Mn(IV) compounds by anaerobic respiration. The formation of huge manganese-rich (carbonate) deposits requires effective manganese redox cycling in an oxygenated atmosphere. However, putative anaerobic pathways such as microbial nitrate-dependent manganese oxidation, anoxygenic photosynthesis and oxidation in ultraviolet light may facilitate manganese cycling even in an early Archean environment, without the availability of oxygen. In addition, manganese carbonates precipitate by microbially induced processes without change of the oxidation state, e.g. by pH shift. Hence, there are several ways how these minerals could have been formed biogenically and deposited in Precambrian sediments. We will summarize microbially induced manganese carbonate deposition in the presence and absence of atmospheric oxygen and we will make some considerations about the biogenic deposition of manganese carbonates in early Archean settings.

This study examines the sintering behavior and properties of Fe-0.8Mn-0.5C manganese powder metallurgy steels. The study focuses on the influence of mode of alloying—admixing using either high-purity electrolytic manganese or medium carbon ferromanganese as well as the fully prealloying of water-atomized powder. Three main aspects were studied during the whole sintering process—microstructure development, interparticle necks evolution, and changes in the behavior of manganese carrier particles during both heating and sintering stages. The prealloyed powder shows considerable improvement in carbon homogenization and interparticle neck development in comparison with admixed materials. The first indication of pearlite for the fully prealloyed material was registered at ~1013 K (740 °C) in comparison with ~1098 K (825 °C) in the case of the admixed systems. The negative effect of the oxidized residuals of manganese carrier particles and high microstructure inhomogeneity, which is a characteristic feature of admixed systems, is reflected in the lower values of the mechanical properties. The worst results in this respect were obtained for the system admixed with electrolytic manganese because of more intensive manganese sublimation and resulting oxidation at lower temperatures. According to the results of X-ray photoelectron spectroscopy and high-resolution scanning electron microscopy and energy dispersive X-ray analyses, the observed high brittleness of admixed materials is connected with intergranular decohesion failure associated with manganese oxide formation on the grain boundaries.

Several Mousterian sites in France have yielded large numbers of small black blocs. The usual interpretation is that these 'manganese oxides' were collected for their colouring properties and used in body decoration, potentially for symbolic expression. Neanderthals habitually used fire and if they needed black material for decoration, soot and charcoal were readily available, whereas obtaining manganese oxides would have incurred considerably higher costs. Compositional analyses lead us to infer that late Neanderthals at Pech-de-l'Azé I were deliberately selecting manganese dioxide. Combustion experiments and thermo-gravimetric measurements demonstrate that manganese dioxide reduces wood's auto-ignition temperature and substantially increases the rate of char combustion, leading us to conclude that the most beneficial use for manganese dioxide was in fire-making. With archaeological evidence for fire places and the conversion of the manganese dioxide to powder, we argue that Neanderthals at Pech-de-l'Azé I used manganese dioxide in fire-making and produced fire on demand. PMID:26922901

This study presents a novel procedure for accelerating methanogenesis from wastewater by adding elemental manganese into the anaerobic digestion system. The results indicated that elemental manganese effectively enhanced both the methane yield and the production rate. Compared to the control test without elemental manganese, the total methane yield and production rate with 4 g/L manganese addition increased 3.4-fold (from 0.89 ± 0.03 to 2.99 ± 0.37 M/gVSS within 120 h) and 4.4-fold (from 6.2 ± 0.1 to 27.2 ± 2.2 mM/gVSS/h), respectively. Besides, more acetate consumption and less propionate generation were observed during the methanogenesis with manganese. Further studies demonstrated that the elemental manganese served as electron donors for the methanogenesis from carbon dioxide, and the final proportion of methane in the total generated gas with 4 g/L manganese addition reached 96.9%, which was 2.1-fold than that of the control (46.6%). PMID:26244609

Several Mousterian sites in France have yielded large numbers of small black blocs. The usual interpretation is that these ‘manganese oxides’ were collected for their colouring properties and used in body decoration, potentially for symbolic expression. Neanderthals habitually used fire and if they needed black material for decoration, soot and charcoal were readily available, whereas obtaining manganese oxides would have incurred considerably higher costs. Compositional analyses lead us to infer that late Neanderthals at Pech-de-l’Azé I were deliberately selecting manganese dioxide. Combustion experiments and thermo-gravimetric measurements demonstrate that manganese dioxide reduces wood’s auto-ignition temperature and substantially increases the rate of char combustion, leading us to conclude that the most beneficial use for manganese dioxide was in fire-making. With archaeological evidence for fire places and the conversion of the manganese dioxide to powder, we argue that Neanderthals at Pech-de-l’Azé I used manganese dioxide in fire-making and produced fire on demand.

The focus of work being performed on Hot Coal Gas Desulfurization is primarily in the use of zinc ferrite and zinc titanate sorbents; however, prior studies at the US Steel Fundamental Research Laboratories in Monroeville, PA, by E.T. Turkdogan indicated that an alternate sorbent, manganese dioxide-containing ore in mixture with alumina (75 wt % ore + 25 wt % Al{sub 2}/O{sub 3}) may be a viable alternative to zinc-based sorbents. Manganese, for example, has a lower vapor pressure in the elemental state than zinc hence it is not as likely to undergo depletion from the sorbent surface upon loading and regeneration cycles. Also manganese oxide is less readily reduced to the elemental state than iron hence the range of reduction potentials for oxygen is somewhat greater than for zinc ferrite. In addition, thermodynamic analysis of the manganese-oxygen-sulfur system shows it to be less amenable to sulfation than zinc ferrite. Potential also exists for utilization of manganese higher temperatures than zinc ferrite or zinc titanate. This presentation gives the thermodynamic background for consideration of manganese-based sorbents as an alternative to zinc ferrite. To date the work which has been in progress for nine months is limited at this stage to thermogravimetric testing of four formulations of manganese-alumina sorbents to determine the optimum conditions of pelletization and induration to produce reactive pellets.

The focus of work being performed on Hot Coal Gas Desulfurization at the Morgantown Energy Technology Center is primarily in the use of zinc ferrite and zinc titanate sorbents; however, prior studies indicated that an alternate sorbent, manganese dioxide-containing ore in mixture with alumina (75 wt % ore + 25 wt % Al{sub 2}O{sub 3}) may be a viable alternative to zinc-based sorbents. Manganese, for example, has a lower vapor pressure in the elemental state than zinc hence it is not as likely to undergo depletion from the sorbent surface upon loading and regeneration cycles. Also manganese oxide is less readily reduced to the elemental state than iron hence the range of reduction potentials for oxygen is somewhat greater than for zinc ferrite. In addition, thermodynamic analysis of the manganese-oxygen-sulfur system shows it to be less amenable to sulfation than zinc ferrite. Potential also exists for utilization of manganese at higher temperatures than zinc ferrite or zinc titanate. This annual topical report documents progress in pelletizing and testing via thermo-gravimetric analysis of individual pellet formulations of manganese ore/alumina combinations and also manganese carbonate/alumina with two binders, dextrin and bentonite.

Manganese is a vital nutrient and is maintained at an optimal level (2.5–5 mg/day) in human body. Chronic exposure to manganese is associated with neurotoxicity and correlated with the development of various neurological disorders such as Parkinson's disease. Oxidative stress mediated apoptotic cell death has been well established mechanism in manganese induced toxicity. Oxidative stress has a potential to alter the epigenetic mechanism of gene regulation. Epigenetic insight of manganese neurotoxicity in context of its correlation with the development of parkinsonism is poorly understood. Parkinson's disease is characterized by the α-synuclein aggregation in the form of Lewy bodies in neuronal cells. Recent findings illustrate that manganese can cause overexpression of α-synuclein. α-Synuclein acts epigenetically via interaction with histone proteins in regulating apoptosis. α-Synuclein also causes global DNA hypomethylation through sequestration of DNA methyltransferase in cytoplasm. An individual genetic difference may also have an influence on epigenetic susceptibility to manganese neurotoxicity and the development of Parkinson's disease. This review presents the current state of findings in relation to role of epigenetic mechanism in manganese induced neurotoxicity, with a special emphasis on the development of Parkinson's disease. PMID:27314012

Transformations in nanosized manganese films are studied by means of optical spectroscopy, microscopy, and gravimetry at different film thicknesses ( d = 4-108 nm) and temperatures of heat treatment ( T = 373-673 K). It is found that the kinetic curves of conversion are satisfactorily described in the terms of linear, inverse logarithmic, cubic, and logarithmic laws. The contact potential difference is measured for Mn and MnO films, and photo EMF is measured for Mn-MnO systems. An energy band diagram is constructed for Mn-MnO systems. A model for the thermal transformation of Mn films is proposed that includes stages of oxygen adsorption, the redistribution of charge carriers in the contact field of Mn-MnO, and manganese(II) oxide formation.

Oneida Lake is a large shallow lake in central New York that is characterized by high algal productivity and concentrated deposits of freshwater manganese nodules. Budgets for Mn in the lake and its tributaries show a net loss of 23 metric tons of manganese within the lake per year with ???95% deposited in manganese nodules and the rest incorporated in the sediments. Erosion of nodules in the shallow well-oxygenated central part of the lake produces fragments of nodules as well as Mn-coated sand grains that are transported to adjacent deeper, more reducing parts of the lake where they sink into the anoxic sediments and MnO2 is reduced to Mn2+. This produces a high concentration of Mn2+ in the pore waters of these sediments and Mn2+ diffuses back into the water column. Growth of manganese nodules in Oneida Lake is characterized by periods of rapid accretion (> 1 mm 100 yr.) alternating with periods of no-growth or erosion. Rapid growth of nodules may be aided by the stripping of Mn from the water column by algae and bacteria. In addition, the high algal productivity of Oneida Lake produces a high-pH high-oxygen environment during the summer months that is maintained throughout the water column in the central part of the lake by almost continuous wind mixing. Thus, the cycle of Mn within the lake involves an interaction of the weather, the biota, the sediments, the nodules, and Mn dissolved in the lake and interstitial waters. ?? 1981.

Manganese (Mn) ranks twelfth among the most exuberant metal present in the earth's crust and finds its imperative application in the manufacturing steel, chemical, tannery, glass, and battery industries. Solubilisation of Mn can be performed by several bacterial strains which are useful in developing environmental friendly solutions for mining activities. The present investigation aims to isolate and characterize Mn solubilising bacteria from low grade ores from Sanindipur Manganese mine of Sundargh district in Odisha state of India. Four morphologically distinct bacterial strains showing visible growth on Mn supplemented plates were isolated. Mn solubilising ability of the bacterial strains was assessed by visualizing the lightening of the medium appearing around the growing colonies. Three isolates were gram negative and rod shaped while the remaining one was gram positive, coccobacilli. Molecular identification of the isolates was carried out by 16S rRNA sequencing and the bacterial isolates were taxonomically classified as Bacillus anthrasis MSB 2, Acinetobacter sp. MSB 5, Lysinibacillus sp. MSB 11, and Bacillus sp. MMR-1 using BLAST algorithm. The sequences were deposited in NCBI GenBank with the accession number KP635223, KP635224, KP635225 and JQ936966, respectively. Manganese solubilisation efficiency of 40, 96, 97.5 and 48.5% were achieved by MMR-1, MSB 2, MSB 5 and MSB 11 respectively. The efficiency of Mn solubilisation is suggested with the help of a pH variation study. The results are discussed in relation to the possible mechanisms involved in Manganese solubilisation efficiency of bacterial isolates. PMID:26471873

The structural and surface properties of manganese and copper-manganese oxides were investigated. The oxides were prepared by the redox-precipitation method. X-ray diffraction and electron microscopy studies evidenced transformation of cryptomelane-type nanoparticles with 1-D channel structure into the large MnO crystallites with regular rippled-like surface patterns under reduction conditions. The development of Cu/CuO nanorods from strongly dispersed species was evidenced. Coper-modified manganese oxides showed good catalytic performance in methanol steam reforming reaction for hydrogen production. Low selectivity to CO was observed in the wide range of temperatures.

Context. Manganese is mainly produced in type II SNe during explosive silicon burning, in incomplete Si-burning regions, and depends on several nucleosynthesis environment conditions, such as mass cut between the matter ejected and falling back onto the remnant, electron and neutron excesses, mixing fallback, and explosion energy. Manganese is also produced in type Ia SNe. Aims: The aim of this work is the study of abundances of the iron-peak element Mn in 56 bulge giants, among which 13 are red clump stars. Four bulge fields along the minor axis are inspected. The study of abundances of Mn-over-Fe as a function of metallicity in the Galactic bulge may shed light on its production mechanisms. Methods: High-resolution spectra were obtained using the FLAMES+UVES spectrograph on the Very Large Telescope. The spectra were obtained within a program to observe 800 stars using the GIRAFFE spectrograph, together with the present UVES spectra. Results: We aim at identifying the chemical evolution of manganese, as a function of metallicity, in the Galactic bulge. We find [Mn/Fe] ~ -0.7 at [Fe/H] ~ -1.3, increasing to a solar value at metallicities close to solar, and showing a spread around - 0.7 ≲ [Fe/H] ≲ -0.2, in good agreement with other work on Mn in bulge stars. There is also good agreement with chemical evolution models. We find no clear difference in the behaviour of the four bulge fields. Whereas [Mn/Fe] vs. [Fe/H] could be identified with the behaviour of the thick disc stars, [Mn/O] vs. [O/H] has a behaviour running parallel, at higher metallicities, compared to thick disc stars, indicating that the bulge enrichment might have proceeded differently from that of the thick disc. Observations collected at the European Southern Observatory, Paranal, Chile (ESO programmes 71.B-0617A, 73.B0074A, and GTO 71.B-0196).Tables 1-6 and Figs. 1-6 are available in electronic form at http://www.aanda.org

The thickest beds of hydrothermal manganese oxides recovered to date from the global ocean were collected from a volcanic cone in the south Pacific. In April 2005, samples were dredged aboard the R.V. Kilo Moana from a volcanic cone on the lower flank of Tulaga seamount (about 2,700 m water depth; 14° 39.222' S; 170° 1.730' W), located 115 km SW of Vailulu'u, the volcanically and hydrothermally active center of the Samoan hotspot. Additional hydrothermal manganese samples were collected off Ofu Island (dredge Alia 107), 72 km to the WSW of Vailulu'u. Manganese-oxide beds up to 9 cm thick are composed of birnessite and 10 Å manganates. Some layers consist of Mn-oxide columnar structures 4 cm long and 1 cm wide, which have not been described previously. The mean Mn and Fe contents of 18 samples are 51 weight percent and 0.76 weight percent, respectively. Elevated concentrations of Li (mean 0.11 wt. percent) are indicators of a hydrothermal origin, and distinguishes these samples, along with the high Mn and low Fe contents, from hydrogenetic Fe-Mn crusts. Other enriched elements include Ba (mean 0.14 percent), Cu (249 ppm), Mo (451 ppm), Ni (400 ppm), Zn (394 ppm), V (214 ppm), and W (132 ppm). Chondrite-normalized REE patterns show large negative Ce anomalies and LREE enrichments, both characteristic of hydrothermal Mn deposits. Small negative Eu anomalies are not typical of hydrothermal deposits and can be explained either by the absence of leaching of plagioclase by the hydrothermal fluids or by the precipitation of Eu-rich minerals, such as barite and anhydrite, at depth. The high base-metal contents indicate that sulfides are not forming deeper in the hydrothermal system or that such deposits are being leached by the ascending fluids. Textures of the thickest Mn deposits indicate that the Mn oxides formed below the seabed from ascending fluids during multiple phases of waxing and waning hydrothermal pulses. The deposits were later exposed at the seafloor by

Profiles of oxygen, soluble and particulate manganese and iron, organic carbon and nitrogen were examined in Lake Superior sediment cores, along with the distribution and abundance of heterotrophic and manganese oxidizing bacteria. Analyses were performed using cores collected with the submersible Johnson Sea Link II. Three cores, exhibiting a range of organic carbon content, were collected from the deepest basin in Lake Superior and the north and south ends of the Caribou trough, and brought to the surface for immediate analysis. Minielectrode profiles of oxygen concentration of the three cores were carried out using a commercially available minielectrode apparatus. Oxygen depletion to less than 1% occurred within 4 cm of the surface for two of the cores, but not until approximately 15 cm for the core from the south basin of the Caribou trough. The three cores exhibited very different profiles of soluble, as well as leachable, manganese and iron, suggesting different degrees of remobilization of these metals in the sediments. Vertical profiles of viable bacteria and Mn oxidizing bacteria, determined by plating and counting, showed that aerobic (and facultatively aerobic) heterotrophic bacteria were present at the highest concentrations near the surface and decreased steadily with depth, while Mn oxidizing bacteria were concentrations primarily at and above the oxic/anoxic interface. Soluble manganese in the pore waters, along with abundant organic carbon, appeared to enhance the presence of manganese oxidizing bacteria, even below the oxic/anoxic interface. Profiles of solid-phase leachable manganese suggested a microbial role in manganese reprecipitation in these sediments.

Unlike other marine-sedimentary manganese ore deposits, which are largely composed of manganese oxides, the primary ore at Molango (Hidalgo State, Mexico) is exclusively manganese carbonate (rhodochrosite, Mn-calcite, kutnahorite). Stable isotope studies of the carbonates from Molango provide critical new information relevant to the controversy over syngenetic and diagenetic models of stratiform manganese deposit formation. Negative ??13C values for carbonates from mineralized zones at Molango are strongly correlated with manganese content both on a whole rock scale and by mineral species. Whole rock ??13C data fall into three groups: high-grade ore = -16.4 to -11.5%.; manganese-rich, sub-ore-grade = -5.2 to 0%.; and unmineralized carbonates = 0 to +2.5%. (PDB). ??18O data show considerable overlap in values among the three groups: +4.8 to -2.8, -5.4 to -0.3%., and -7.4 to +6.2 (PDB), respectively. Isotopic data for individual co-existing minerals suggest a similar separation of ??13C values: ??13C values from calcite range from -1.1 to +0.7%. (PDB), whereas values from rhodochrosite are very negative, -12.9 to -5.5%., and values from kutnahorite or Mn-calcite are intermediate between calcite and rhodochrosite. 13C data are interpreted to indicate that calcite (i.e. unmineralized carbonate) formed from a normal marine carbon reservoir. However, 13C data for the manganese-bearing carbonates suggest a mixed seawater and organic source of carbon. The presence of only trace amounts of pyrite suggests sulfate reduction may have played a minor part in oxidizing organic matter. It is possible that manganese reduction was the predominant reaction that oxidized organic matter and that it released organic-derived CO2 to produce negative ??13C values and manganese carbonate mineralization. ?? 1988.

Manganese is an essential trace element, whose intracellular levels need to be carefully regulated. Mn(2+) acts as a cofactor for many enzymes and excess of Mn(2+) is toxic. Alterations in Mn(2+) homeostasis affect metabolic functions and mutations in the human Mn(2+)/Ca(2+) transporter ATP2C1 have been linked to Hailey-Hailey disease. By deletion of the yeast orthologue PMR1 we have studied the impact of Mn(2+) on cell cycle progression and show that an excess of cytosolic Mn(2+) alters S-phase transit, induces transcriptional up-regulation of cell cycle regulators, bypasses the need for S-phase cell cycle checkpoints and predisposes to genomic instability. On the other hand, we find that depletion of the Golgi Mn(2+) pool requires a functional morphology checkpoint to avoid the formation of polyploid cells. PMID:22493290

Neurodegenerative diseases affect a significant portion of the aging population. Several lines of evidence suggest a positive association between environmental exposures, which are common and cumulative in a lifetime, and development of neurodegenerative diseases. Environmental or occupational exposure to manganese (Mn) has been implicated in neurodegeneration due to its ability to induce mitochondrial dysfunction, oxidative stress, and α-synuclein (α-Syn) aggregation. The role of the α-Syn protein vis-a-vis Mn is controversial, as it seemingly plays a duplicitous role in neuroprotection and neurodegeneration. α-Syn has low affinity for Mn, however an indirect interaction cannot be ruled out. In this review we will examine the current knowledge surrounding the interaction of α-Syn and Mn in neurodegenerative process. PMID:27540354

Neurodegenerative diseases affect a significant portion of the aging population. Several lines of evidence suggest a positive association between environmental exposures, which are common and cumulative in a lifetime, and development of neurodegenerative diseases. Environmental or occupational exposure to manganese (Mn) has been implicated in neurodegeneration due to its ability to induce mitochondrial dysfunction, oxidative stress, and α-synuclein (α-Syn) aggregation. The role of the α-Syn protein vis-a-vis Mn is controversial, as it seemingly plays a duplicitous role in neuroprotection and neurodegeneration. α-Syn has low affinity for Mn, however an indirect interaction cannot be ruled out. In this review we will examine the current knowledge surrounding the interaction of α-Syn and Mn in neurodegenerative process. PMID:27540354

Manganese (Mn) is an essential heavy metal that is naturally found in the environment. Daily intake through dietary sources provides the necessary amount required for several key physiological processes, including antioxidant defense, energy metabolism, immune function and others. However, overexposure from environmental sources can result in a condition known as manganism that features symptomatology similar to Parkinson's disease (PD). This disorder presents with debilitating motor and cognitive deficits that arise from a neurodegenerative process. In order to maintain a balance between its essentiality and neurotoxicity, several mechanisms exist to properly buffer cellular Mn levels. These include transporters involved in Mn uptake, and newly discovered Mn efflux mechanisms. This review will focus on current studies related to mechanisms underlying Mn import and export, primarily the Mn transporters, and their function and roles in Mn-induced neurotoxicity. PMID:25982296

During the hydrometallurgical extraction of zinc by electrowinning process, a hazardous solid waste called anode mud is generated. It contains large quantity of manganese oxides (55-80%) and lead dioxide (6-16%). Due to the presence of a large quantity of lead, the anode mud waste is considered hazardous and has to be disposed of in secure landfills, which is costly, wastes available manganese and valuable land resources. For recovery of manganese content of anode mud, a process comprising of carbothermal treatment using low density oil (LDO) followed by sulphuric acid leaching is developed. PMID:21115220

Background: The literature on manganese (Mn) is dominated by occupational exposures of adults exposed often to high levels without protection. Neuropsychological adverse health effects are similar to Parkinson’s Disease with psychomotor slowing, tremor, cognitive and mood ...

The Cuyuna range, located in east-central Minnesota, consists of a sequence of argillite, siltstone, iron-formation, graywacke, slate, and quartzite of early Proterozoic age. Manganese-bearing materials occur within the iron-rich strata of the Trommald Formation and the Rabbit Lake Formation. Computer-assisted resource estimates, based on exploration drill hole information, indicate that the Cuyuna range contains a minimum of 176 million metric tons (MMT) of marginally economic manganiferous rock with an average grade of 10.46 weight percent manganese. The calculated 18.5 MMT of manganese on the Cuyuna range could supply this country's needs for this important and strategic metal for nearly 14 years. An additional resource of 6.9 MMT of manganese metal is available in the lower grade deposits The vast majority of these calculated resources are extractable by current surface mining techniques.

Sulfate reduction is considered the primary pathway for organic carbon remineralization on the northern Gulf of Mexico Louisiana continental shelf (LCS) where bottom waters are seasonally hypoxic, yet limited information is available on the importance of iron and manganese cyclin...

U-silicide or U-nitride coated U-Mo particle dispersion fuel in Al (U-Mo/Al) was in-pile tested to examine the effectiveness of the coating as a diffusion barrier between the U-7Mo fuel kernels and Al matrix. This paper reports the PIE data and analyses focusing on the effectiveness of the coating in terms of interaction layer (IL) growth and general fuel performance. The U-silicide coating showed considerable success, but it also provided evidence for additional improvement for coating process. The U-nitride coated specimen showed largely inefficient results in reducing IL growth. From the test, important observations were also made that can be utilized to improve U-Mo/Al fuel performance. The heating process for coating turned out to be beneficial to suppress fuel swelling. The use of larger fuel particles confirmed favorable effects on fuel performance.

When CaF2 molecules are deposited on Si(1 1 4)-2 × 1 held at 500 °C, two kinds of isolated and symmetric Ca-silicide units are initially formed. With increasing CaF2 deposition to 0.4 ML, instead of the terrace being filled with them, a trench composed of (1 1 3) and (1 1 7) facets appears on the surface as a result of substrate etching induced by dissociated F atoms. Selectively on this (1 1 3) facet, a 2 × 2 CaF overlayer is formed uniformly. In the present studies, using scanning tunneling microscopy and synchrotron photoemission spectroscopy, the origins of such isolation of Ca-silicide units on the (1 1 4) terrace as well as selective adsorption of CaF on the (1 1 3) facet have been disclosed.

We report a large negative magnetoresistance in Manganese-substituted Zinc Oxide thin films. This anomalous effect was found to appear in oxygen-deficient films and to increase with the concentration of Manganese. By combining magnetoresistive measurements with magneto-photoluminescence, we demonstrate that the effect can be explained as the result of a magnetically induced transition from hopping to band conduction where the activation energy is caused by the sp-d exchange interaction. PMID:25783664

This paper demonstrates that manganese oxides can initiate the formation of methyl iodide, a volatile compound that participates to the input of iodine into the atmosphere. The formation of methyl iodide was investigated using a natural manganese oxide in batch experiments for different conditions and concentrations of iodide, natural organic matter (NOM) and manganese oxide. Methyl iodide was formed at concentrations manganese dioxide in the presence of iodide. However, the implication of elemental iodine cannot be excluded at acidic pH. Manganese oxides can then participate with ferric oxides to the formation of methyl iodide in soils and sediments. The formation of methyl iodide is unlikely in technical systems such as drinking water treatment i.e. for ppt levels of iodide and low contact times with manganese oxides. PMID:20580399

Emara, A. M., El-Ghawabi, S. H., Madkour, O. I., and El-Samra, G. H. (1971). Brit. J. industr. Med., 28, 78-82. Chronic manganese poisoning in the dry battery industry. A survey was carried out on 36 workers in the dry battery industry exposed to dust containing 65 to 70% manganese oxide. Eight (22·2%) were found to have neuropsychiatric manifestations, six (16·6%) had chronic manganese psychosis, one had left hemi-parkinsonism, and one had left choreoathetosis. An environmental study revealed a high concentration of manganese dust at the main working areas, far exceeding the accepted MAC. The manganese level in blood was almost within the normal range. Coproporphyrin in urine was normal. The electroencephalogram was abnormal in only two of the affected workers (25%) but there was no association between this and the clinical manifestations or duration of exposure. The concentration of manganese dust in air showed some association with the prevalence and rapidity of effect on workers according to their occupation. However, individual susceptibility was apparent. The shortest latent period was one year. PMID:5101169

Accumulation of aggregates rich in an abnormally folded form of the prion protein characterize the neurodegeneration caused by transmissible spongiform encephalopathies (TSEs). The molecular triggers of plaque formation and neurodegeneration remain unknown, but analyses of TSE-infected brain homogenates and preparations enriched for abnormal prion protein suggest that reduced levels of copper and increased levels of manganese are associated with disease. The objectives of this study were to: (1) assess copper and manganese levels in healthy and TSE-infected Syrian hamster brain homogenates; (2) determine if the distribution of these metals can be mapped in TSE-infected brain tissue using X-ray photoelectron emission microscopy (X-PEEM) with synchrotron radiation; and (3) use X-PEEM to assess the relative amounts of copper and manganese in prion plaques in situ. In agreement with studies of other TSEs and species, we found reduced brain levels of copper and increased levels of manganese associated with disease in our hamster model. We also found that the in situ levels of these metals in brainstem were sufficient to image by X-PEEM. Using immunolabeled prion plaques in directly adjacent tissue sections to identify regions to image by X-PEEM, we found a statistically significant relationship of copper-manganese dysregulation in prion plaques: copper was depleted whereas manganese was enriched. These data provide evidence for prion plaques altering local transition metal distribution in the TSE-infected central nervous system.

Romans, Jews, Arabs and Christians built the ancient city of Toledo (Spain) with bricks as the main construction material. Manganese micro-nodules (circa 2 microm in diameter) have grown under the external bio-film surface of the bricks. Recent anthropogenic activities such as industrial emissions, foundries, or traffic and housing pollution have further altered these old bricks. The energy-dispersive X-ray microanalyses (XPS) of micro-nodules show Al, Si, Ca, K, Fe and Mn, with some carbon species. Manganese atoms are present only as Mn(4+) and iron as Fe(3+) (FeOOH-Fe(2)O(3) mixtures). The large concentration of alga biomass of the River Tagus and the Torcón and Guajaraz reservoirs suggest manganese micro-nodules are formed either from water solutions rich in anthropogenic MnO(4)K in a reduction environment (from Mn(7+) to Mn(4+)) or by oxidation mechanisms from dissolved Mn(2+) (from Mn(2+) to Mn(4+)) linked to algae biofilm onto the ancient brick surfaces. Ancient wall surfaces were also studied by scanning electron microscopy (SEM-EDS) and X-ray diffraction (XRD). Chemical and biological analyses of the waters around Toledo are also analysed for possible sources of manganese. Manganese micro-nodules on ancient brick walls are good indicators of manganese pollution. PMID:12526915

Epitaxial iron silicide nanostructures are grown by solid phase epitaxy on Si(0 0 1) and Si(1 1 1), and by reactive deposition epitaxy on Si(0 0 1) substrates. The formation process is monitored by reflection high-energy electron diffraction. The morphology, size, and electrical properties of the nanoparticles are investigated by scanning electron microscopy, by electrically active scanning probe microscopy, and by confocal Raman spectroscopy. The results show that the shape, size, orientation, and density of the nanoobjects can be tuned by self-assembly, controlled by the lattice misfit between the substrates and iron silicides. The size distribution and shape of the grown nanoparticles depend on the substrate orientation, on the initial thickness of the evaporated iron, on the temperature and time of the annealing, and on the preparation method. The so-called Ostwald ripening phenomena, which state that the bigger objects develop at the expense of smaller ones, controls the density of the nanoparticles. Raman spectra show the bigger objects do not contain β-FeSi2 phase. The different shape nanoparticles exhibit small, about 100 mV barrier compared to the surrounding silicon. The local leakage current of the samples measured by conductive AFM using a Pt coated Si tip is localized in a few nanometers size sites, and the sites which we assume are very small silicide nanoparticles or point defects.

Combined scanning tunneling microscopy, Auger electron spectroscopy, and surface magneto-optic Kerr effect studies were employed to study the microscopic structures and magnetic properties for ultrathin Co/√(3)×√(3)R30°-Ag/Si(111). As the annealing temperature increases, the upward diffusion of Si atoms and formation of Co silicides occurs at temperature above 400 K. Below 600 K, the √(3)×√(3)R30°-Ag/Si(111) surface structure persists. We propose an interaction transferring mechanism of Si atoms across the √(3)×√(3)R30°-Ag layer. The upward transferred Si atoms react with Co atoms to form Co silicide. The step height across the edge of the island, a separation of 0.75 nm from the analysis of the 2 × 2 structure, and the calculations of the normalized Auger signal serve as strong evidences for the formation of CoSi{sub 2} at the interface. The interaction transferring mechanism for Si atoms enhances the possibility of interactions between Co and Si atoms. The smoothness of the surface is advantage for that the easy axis of magnetization for Co/√(3)×√(3)R30°-Ag/Si(111) is in the surface plane. This provides a possible way of growing flat magnetic layers on silicon substrate with controllable silicide formation and shows potential applications in spintronics devices.

A halide-activated cementation pack involving elemental Al and Cr powders has been used to achieve surface compositions of approximately Fe{sub 3}Al plus several percent Cr for low alloy steels (T11, T2 and T22) and medium carbon steel (1045 steel). A two-step treatment at 925 C and 1150 C yields the codeposition and diffusion of aluminum and chromium to form dense and uniform ferrite coatings of about 400 {micro}m thickness, while preventing the formation of a blocking chromium carbide at the substrate surfaces. Upon cyclic oxidation in air at 700 C, the coated steel exhibits a negligible 0.085 mg/cm{sup 2} weight gain for 1900 one-hour cycles. Virtually no attack was observed on coated steels tested at ABB in simulated boiler atmospheres at 500 C for 500 hours. But coatings with a surface composition of only 8 wt% Al and 6 wt% Cr suffered some sulfidation attack in simulated boiler atmospheres at temperatures higher than 500 C for 1000 hours. Two developmental Cr-Zr based Laves phase alloys (CN129-2 and CN117(Z)) were silicide/germanide coated. The cross-sections of the Ge-doped silicide coatings closely mimicked the microstructure of the substrate alloys. Cyclic oxidation in air at 1100 C showed that the Ge-doped silicide coating greatly improved the oxidation resistance of the Cr-Zr based alloys.

The manganse bioleaching mechanism by a manganese-resistant strain Fusarium sp. was investigated, through analyzing the bioleaching rate and manganese-electrolytic residue characterizations with the presence of Fusarium sp. and with the addition of organic acids. Special attention was paid to explore the relationship among the manganese's leaching rate, pH, and organic acid concentration during Fusarium sp. bioleaching process. The research results showed that, with the addition of Fusarium sp., some looser and more porous manganese-electrolytic residues could be obtained. And after 47 hours, the leaching rate reached to 84% which was 2.30 times higher than that leached by individual organic acid even after 130 hours; the leaching rate of manganese and the concentrations of organic acids increased at the initial stage and then decreased, while pH was the reversed. Additionally, the concentration of Succinic acid and L-Malic acid reached their crest value (11.12 g/L and 10.23 g/L) at 57 and 62 hours respectively. Yet the pH reached the lowest (4.09) at 29 h, which implied that, Fusarium sp. and organic acid produced played an important role in the leaching of manganese, leading to a high-efficiency and time-saving process. However, due to the high density of manganese-electrolytic residue and the concurrence of the produce and consumption of organic acid together with the adsorption and complexation, the relationship among the extraction rate for manganese ion, pH, and the concentration of organic acid produced could not be described by simple linear correlation and the leaching rate decreased significantly in the later stage. PMID:22165242

Manganese atoms have long been implicated as essential ingredients in photosynthetic oxygen evolution. Heretofore they have eluded direct observation. We report the first direct observation, by X-ray Absorption Spectroscopy, of the Mn sites in chloroplasts isolated from Spinacia oleracea. The manganese in chlorplasts is commonly thought to exist in two pools. The major pool, corresponding to two-thirds of the manganese, can be reversibly released with concomitant loss of oxygen evolving capacity, and has thus come to be assigned as the active pool. The role of the remanant one-third, or tightly bound pool is moot. Our analysis of the Extended X-ray Absorption Fine Structure of the active pool is consistent with a bridged dimeric structure involving two manganese atoms separated by about 2.7 {Angstroms}. The distance between manganese and bridging ligands is about 1.8 {Angstrom}. Analysis of the edge region suggests that the manganese in the active pool exists in oxidation states somewhat higher than Mn(II).

Reduction of superoxide (O{sub 2}{sup -}) by manganese-containing superoxide dismutase occurs through either a 'prompt protonation' pathway, or an 'inner-sphere' pathway, with the latter leading to formation of an observable Mn-peroxo complex. We recently reported that wild-type (WT) manganese superoxide dismutases (MnSODs) from Saccharomyces cerevisiae and Candida albicans are more gated toward the 'prompt protonation' pathway than human and bacterial MnSODs and suggested that this could result from small structural changes in the second coordination sphere of manganese. We report here that substitution of a second-sphere residue, Tyr34, by phenylalanine (Y34F) causes the MnSOD from S. cerevisiae to react exclusively through the 'inner-sphere' pathway. At neutral pH, we have a surprising observation that protonation of the Mn-peroxo complex in the mutant yeast enzyme occurs through a fast pathway, leading to a putative six-coordinate Mn3+ species, which actively oxidizes O{sub 2}{sup -} in the catalytic cycle. Upon increasing pH, the fast pathway is gradually replaced by a slow proton-transfer pathway, leading to the well-characterized five-coordinate Mn{sup 3+}. We here propose and compare two hypothetical mechanisms for the mutant yeast enzyme, diffeeing in the structure of the Mn-peroxo complex yet both involving formation of the active six-coordinate Mn{sup 3+} and proton transfer from a second-sphere water molecule, which has substituted for the -OH of Tyr34, to the Mn-peroxo complex. Because WT and the mutant yeast MnSOD both rest in the 2+ state and become six-coordinate when oxidized up from Mn{sup 2+}, six-coordinate Mn{sup 3+} species could also actively function in the mechanism of WT yeast MnSODs.

Reduction of superoxide () by manganese-containing superoxide dismutase occurs through either a “prompt protonation” pathway, or an “inner-sphere” pathway, with the latter leading to formation of an observable Mn-peroxo complex. We recently reported that wild-type (WT) manganese superoxide dismutases (MnSODs) from Saccharomyces cerevisiae and Candida albicans are more gated toward the “prompt protonation” pathway than human and bacterial MnSODs and suggested that this could result from small structural changes in the second coordination sphere of manganese. We report here that substitution of a second-sphere residue, Tyr34, by phenylalanine (Y34F) causes the MnSOD from S. cerevisiae to react exclusively through the “inner-sphere” pathway. At neutral pH, we have a surprising observation that protonation of the Mn-peroxo complex in the mutant yeast enzyme occurs through a fast pathway, leading to a putative six-coordinate Mn3+ species, which actively oxidizes in the catalytic cycle. Upon increasing pH, the fast pathway is gradually replaced by a slow proton-transfer pathway, leading to the well-characterized five-coordinate Mn3+. We here propose and compare two hypothetical mechanisms for the mutant yeast enzyme, differing in the structure of the Mn-peroxo complex yet both involving formation of the active six-coordinate Mn3+ and proton transfer from a second-sphere water molecule, which has substituted for the ─OH of Tyr34, to the Mn-peroxo complex. Because WT and the mutant yeast MnSOD both rest in the 2+ state and become six-coordinate when oxidized up from Mn2+, six-coordinate Mn3+ species could also actively function in the mechanism of WT yeast MnSODs. PMID:22908245

Previous studies in neonatal and suckling animals showed that immature animals have a greatly diminished capacity to excrete manganese and therefore were considered to be unable to regulate tissue manganese concentrations. In contrast, the present studies indicate that suckling rats have the capacity to excrete excess manganese at rates nearly comparable to those of adults. Eight- to 10-day-old rats given a tracer dose of /sup 54/MnCl/sub 2/ (essentially carrier free), either via gavage or by intraperitoneal injection showed little elimination of the /sup 54/Mn until the 18-19th day of life, when there was an abrupt increase in the rate of the metal's excretion. However, when manganese was given in doses of 1 and 10 mg/kg, the young animals excreted from 30-70% of the dose in only 4 days, at which time a new rate of excretion was achieved. This enhanced rate of excretion remained constant until the 18-19th day of life, when it was again accelerated. Biliary excretion of manganese, the primary route for the elimination of the metal, was only 30-60% lower in 14-day-old rats compared with adults at doses ranging from tracer to 10 mg /sup 54/Mn/kg. For both the 14-day-old and adult rats, an apparent biliary transport maximum was reached at a dose of 10 mg Mn/kg. These studies indicate that the excretory pathways for manganese are well developed in the neonatal rat. The avid retention of tracer quantities of manganese by the neonate may be a consequence of the scarcity of this essential trace metal in its diet.

The mitochondrion is vital for many metabolic pathways in the cell, contributing all or important constituent enzymes for diverse functions such as β-oxidation of fatty acids, the urea cycle, the citric acid cycle, and ATP synthesis. The mitochondrion is also a major site of reactive oxygen species (ROS) production in the cell. Aberrant production of mitochondrial ROS can have dramatic effects on cellular function, in part, due to oxidative modification of key metabolic proteins localized in the mitochondrion. The cell is equipped with myriad antioxidant enzyme systems to combat deleterious ROS production in mitochondria, with the mitochondrial antioxidant enzyme manganese superoxide dismutase (MnSOD) acting as the chief ROS scavenging enzyme in the cell. Factors that affect the expression and/or the activity of MnSOD, resulting in diminished antioxidant capacity of the cell, can have extraordinary consequences on the overall health of the cell by altering mitochondrial metabolic function, leading to the development and progression of numerous diseases. A better understanding of the mechanisms by which MnSOD protects cells from the harmful effects of overproduction of ROS, in particular, the effects of ROS on mitochondrial metabolic enzymes, may contribute to the development of novel treatments for various diseases in which ROS are an important component. PMID:22072939

Manganese peroxidases (MnPs) are key players in the ligninolytic system of white rot fungi. In Pleurotus ostreatus (the oyster mushroom) these enzymes are encoded by a gene family comprising nine members, mnp1 to -9 (mnp genes). Mn(2+) amendment to P. ostreatus cultures results in enhanced degradation of recalcitrant compounds (such as the azo dye orange II) and lignin. In Mn(2+)-amended glucose-peptone medium, mnp3, mnp4, and mnp9 were the most highly expressed mnp genes. After 7 days of incubation, the time point at which the greatest capacity for orange II decolorization was observed, mnp3 expression and the presence of MnP3 in the extracellular culture fluids were predominant. To determine the significance of MnP3 for ligninolytic functionality in Mn(2+)-sufficient cultures, mnp3 was inactivated via the Δku80 strain-based P. ostreatus gene-targeting system. In Mn(2+)-sufficient medium, inactivation of mnp3 did not significantly affect expression of nontargeted MnPs or their genes, nor did it considerably diminish the fungal Mn(2+)-mediated orange II decolorization capacity, despite the significant reduction in total MnP activity. Similarly, inactivation of either mnp4 or mnp9 did not affect orange II decolorization ability. These results indicate functional redundancy within the P. ostreatus MnP gene family, enabling compensation upon deficiency of one of its members. PMID:23377936

Manganese (Mn) is an essential trace metal found in all tissues, and it is required for normal amino acid, lipid, protein, and carbohydrate metabolism. While Mn deficiency is extremely rare in humans, toxicity due to overexposure of Mn is more prevalent. The brain appears to be especially vulnerable. Mn neurotoxicity is most commonly associated with occupational exposure to aerosols or dusts that contain extremely high levels (> 1-5 mg Mn/m3) of Mn, consumption of contaminated well water, or parenteral nutrition therapy in patients with liver disease or immature hepatic functioning such as the neonate. This review will focus primarily on the neurotoxicity of Mn in the neonate. We will discuss putative transporters of the metal in the neonatal brain and then focus on the implications of high Mn exposure to the neonate focusing on typical exposure modes (e.g., dietary and parenteral). Although Mn exposure via parenteral nutrition is uncommon in adults, in premature infants, it is more prevalent, so this mode of exposure becomes salient in this population. We will briefly review some of the mechanisms of Mn neurotoxicity and conclude with a discussion of ripe areas for research in this underreported area of neurotoxicity. PMID:17084903

We propose to obtain a carefully planned set of multiple high dispersion exposures of three MercuryManganese stars in both the SWP and LWP cameras. These observations will be coadded to increase the S/N ratio so that accurate elemental abundances can be derived for these examples of HgMn stars, each of which represents some extreme class aspect. This will increase of sample of HgMn stars from four to seven. Of particular interest are the abundances of N and Co in which some HgMn stars have shown remarkable underabundances. Comparison of the UV and optical spectra features due to light elements such as N (and C and 0) provide an observational framework to test NLTE models such as those of Takada (1993). This work has already shed some light on some of earlier findings for normal stars. The ability to accurately determine the surface chemical composition of the late B stars through such studies will lead to better tests for theories purporting to explain the origin of the chemical peculiarities seen in this temperature domain.

Manganese (Mn) is a required cofactor for all forms of life. Given the importance of Mn to bacteria, the host has devised strategies to sequester Mn from invaders. In the macrophage phagosome, NRAMP1 removes Mn and other essential metals to starve intracellular pathogens; in the extracellular space, calprotectin chelates Mn and Zn. Calprotectin-mediated Mn sequestration is a newly appreciated host defense mechanism, and recent findings are highlighted herein. In order to acquire Mn when extracellular concentrations are low, bacteria have evolved efficient Mn acquisition systems that are under elegant transcriptional control. To counteract Mn overload, some bacteria possess Mn-specific export systems that are important in vivo, presumably for control of intracellular Mn levels. Mn transporters, their transcriptional regulators and some Mn-requiring enzymes are necessary for virulence of certain bacterial pathogens, as revealed by animal models of infection. Furthermore, Mn is an important facet of the cellular response to oxidative stress, a host antibacterial strategy. The battle for Mn between host and pathogen is now appreciated to be a major determinant of the outcome of infection. In this MicroReview, the contribution of Mn to the host-pathogen interaction is reviewed, and key questions are proposed for future study. PMID:25898914

Manganese peroxidases (MnPs) are key players in the ligninolytic system of white rot fungi. In Pleurotus ostreatus (the oyster mushroom) these enzymes are encoded by a gene family comprising nine members, mnp1 to -9 (mnp genes). Mn2+ amendment to P. ostreatus cultures results in enhanced degradation of recalcitrant compounds (such as the azo dye orange II) and lignin. In Mn2+-amended glucose-peptone medium, mnp3, mnp4, and mnp9 were the most highly expressed mnp genes. After 7 days of incubation, the time point at which the greatest capacity for orange II decolorization was observed, mnp3 expression and the presence of MnP3 in the extracellular culture fluids were predominant. To determine the significance of MnP3 for ligninolytic functionality in Mn2+-sufficient cultures, mnp3 was inactivated via the Δku80 strain-based P. ostreatus gene-targeting system. In Mn2+-sufficient medium, inactivation of mnp3 did not significantly affect expression of nontargeted MnPs or their genes, nor did it considerably diminish the fungal Mn2+-mediated orange II decolorization capacity, despite the significant reduction in total MnP activity. Similarly, inactivation of either mnp4 or mnp9 did not affect orange II decolorization ability. These results indicate functional redundancy within the P. ostreatus MnP gene family, enabling compensation upon deficiency of one of its members. PMID:23377936

Manganese (Mn), is a trace metal required for normal physiological processes in humans. Mn levels are tightly regulated, as high levels of Mn result in accumulation in the brain and cause a neurological disease known as manganism. Manganism shares many similarities with Parkinson’s disease (PD), both at the physiological level and the cellular level. Exposure to high Mn-containing environments increases the risk of developing manganism. Mn is absorbed primarily through the intestine and then released in the blood. Excessive Mn is secreted in the bile and excreted in feces. Mn enters and exits cells through a number of non-specific importers localized on the cell membrane. Mutations in one of the Mn exporters, SLC30A10 (solute carrier family 30, member 10), result in Mn induced toxicity with liver impairments and neurological dysfunction. Four PD genes have been identified in connection to regulation of Mn toxicity, shedding new light on potential links between manganism and PD. PMID:25136353

This study examined the abiotic transformation kinetics of pentachlorophenol (PCP) by manganese dioxide (MnO2) at different solution chemistry and initial concentrations of PCP and MnO2. The measured PCP transformation rates were found to be on the order of 1.07 with respect to [PCP] and 0.91 and 0.87 with respect to [MnO2] and [H+], respectively. Dissolved Mn2+ and Ca2+ as background electrolytes considerably decreased the reaction rate because of their adsorption and hence blocking of active sites on MnO2 surfaces. The dechlorination number, 0.59 chloride ions per transformed PCP after a 1-h reaction, suggests that a fraction of the transformed PCP was not dechlorinated and may be coupled directly to dimeric products. Gas chromatography/ mass spectrometry and liquid chromatography/mass spectrometry/mass spectrometry techniques were used to identify two isomeric nonachlorohydroxybiphenylethers as major products and 2,3,5,6-tetrachloro-1,4-hydroquinone and tetrachlorocatechol as minor products. Product identification suggested that the reaction may include two parallel reactions to form either dimers or 2,3,5,6-tetrachloro-1,4-hydroquinone and tetrachlorocatechol via simultaneous dehydrochlorination and hydroxylation. PMID:17089714

The mitochondrion is vital for many metabolic pathways in the cell, contributing all or important constituent enzymes for diverse functions such as β-oxidation of fatty acids, the urea cycle, the citric acid cycle, and ATP synthesis. The mitochondrion is also a major site of reactive oxygen species (ROS) production in the cell. Aberrant production of mitochondrial ROS can have dramatic effects on cellular function, in part, due to oxidative modification of key metabolic proteins localized in the mitochondrion. The cell is equipped with myriad antioxidant enzyme systems to combat deleterious ROS production in mitochondria, with the mitochondrial antioxidant enzyme manganese superoxide dismutase (MnSOD) acting as the chief ROS scavenging enzyme in the cell. Factors that affect the expression and/or the activity of MnSOD, resulting in diminished antioxidant capacity of the cell, can have extraordinary consequences on the overall health of the cell by altering mitochondrial metabolic function, leading to the development and progression of numerous diseases. A better understanding of the mechanisms by which MnSOD protects cells from the harmful effects of overproduction of ROS, in particular, the effects of ROS on mitochondrial metabolic enzymes, may contribute to the development of novel treatments for various diseases in which ROS are an important component. PMID:22072939

Chenopodium ambrosioides L. can tolerate high concentrations of manganese and has potential for its use in the revegetation of manganese mine tailings. Following a hydroponic investigation, transmission electron microscopy (TEM)-energy disperse spectroscopy (EDS) was used to study microstructure changes and the possible accumulation of Mn in leaf cells of C. ambrosioides in different Mn treatments (200, 1000, 10000 μmol·L(-1)). At 200 μmol·L(-1), the ultrastructure of C. ambrosioides was clearly visible without any obvious damage. At 1000 μmol·L(-1), the root, stem and leaf cells remained intact, and the organelles were clearly visible without any obvious damage. However, when the Mn concentration exceeded 1000 μmol·L(-1) the number of mitochondria in root cells decreased and the chloroplasts in stem cells showed a decrease in grana lamellae and osmiophilic granules. Compared to controls, treatment with 1000 μmol·L(-1) or 10000 μmol·L(-1) Mn over 30 days, gave rise to black agglomerations in the cells. At 10000 μmol·L(-1), Mn was observed to form acicular structures in leaf cells and intercellular spaces, which may be a form of tolerance and accumulation of Mn in C. ambrosioides. This study has furthered the understanding of Mn tolerance mechanisms in plants, and is potential for the revegetation of Mn-polluted soils. PMID:26696389

Introduction Manganese regulates many enzymes and is essential for normal development and body function. Chronic manganese intoxication has an insidious and progressive course and usually starts with complaints of headache, fatigue, sleep disturbances, irritability and emotional instability. Later, several organ systems may be affected and, due to neurotoxicity, an atypical parkinsonian syndrome may emerge. With regard to neuropsychiatry, an array of symptoms may develop up to 30 years after intoxication, of which gait and speech abnormalities, cognitive and motor slowing, mood changes and hallucinations are the most common. Psychotic phenomena are rarely reported. Case presentation We describe the case of a 49-year-old Caucasian man working as a welder who was referred to our facility for evaluation of acute paranoid psychotic behavior. Our patient's medical history made no mention of any somatic complaints or psychiatric symptoms, and he had been involved in a professional career as a metalworker. On magnetic resonance imaging scanning of his brain, a bilateral hyperdensity of the globus pallidus, suggestive for manganese intoxication, was found. His manganese serum level was 52 to 97 nmol/L (range: 7 to 20 nmol/L). A diagnosis of organic psychotic disorder due to manganese overexposure was made. His psychotic symptoms disappeared within two weeks of treatment with low-dose risperidone. At three months later, serum manganese was decreased to slightly elevated levels and the magnetic resonance imaging T1 signal intensity was reduced. No signs of Parkinsonism were found and a definite diagnosis of manganese-induced apathy syndrome was made. Conclusion Although neuropsychiatric and neurological symptoms caused by (chronic) manganese exposure have been reported frequently in the past, in the present day the disorder is rarely diagnosed. In this report we stress that manganese intoxication can still occur, in our case in a confined-space welder, and may present

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Manganese is an essential trace element for the development and function of the central nervous system. Alterations in manganese concentrations, whether excessive or deficient, can be accompanied by convulsions. This article represents a systematic review of available quantitative evidence that might clarify this issue. We searched The Cochrane Library, Medline and LILACS databases from January 1966 through June 2006 and reviewed all resulting English and Spanish language publications, as well as those possibly relevant in other languages based on their abstracts. The final selection included for this review comprises all investigations in humans and animals that compared manganese levels in any tissue of a group with spontaneous or induced convulsions (with or without antiepileptic treatment) and a convulsion-free control group. The literature search identified thirteen publications since then relevant to the issue, four of which failed to meet our criteria for inclusion. Of the remaining nine, six were in humans and three in rodents. At present, there is no satisfactory explanation for the relationship between low manganese levels and the presence of convulsions. There is a documented correlation between low blood manganese levels and the presence of convulsions in both humans and animals. The lack of evidence indicating whether this is a cause or an effect of the convulsions clearly justifies more detailed follow-up investigations in humans. PMID:17166592

In the oceans, naturally occurring manganese (Mn) is released from the sediments during events of hypoxia. While neuro- and immuno-toxic effects of bioavailable manganese are well documented for crustaceans, studies of similar effects of manganese on other marine invertebrates are comparatively few. Here, we developed a new functional test "the repeated turning assay" to investigate if manganese exposure at ∼12 mg L(-1) affected motoric behaviour of two asteroid echinoderms, the Common sea star, Asterias rubens, and the Black brittle star, Ophiocomina nigra. By measuring of the turning-over capacity, from dorsal to ventral position, after one and two weeks of manganese exposure, we showed that for both species Mn exposure significantly delayed the ability to turn. After a recovery period of two weeks, the capacity of turning-over was not restored to that of unexposed animals neither for A. rubens nor for O. nigra. Further investigation of sea stars showed that Mn accumulated ∼5 fold in the tube feet, organs involved in their turning-over activity, and the high concentration remained after the recovery period. In the tube feet we also recorded an increased activity of acetylcholinesterase (AChE), here used as a proxy for neuromuscular disturbances. The results indicated that Mn induces neuromuscular disturbance in echinoderms which is important news, given that previous studies have concluded that adult echinoderms are relatively tolerant to Mn. PMID:26254768

Manganese belongs to a group of agents called "transitional metals" that are known to induce occupational asthma. However, well-documented cases of manganese-induced asthma have been lacking thus far. We have discussed a case of a 42-year-old non-smoking welder with work-related dyspnea. A number of clinical procedures were performed including clinical examination, routine laboratory tests, total serum IgE, skin prick tests to common aeroallergens and manganese nitrate, resting spirometry test, histamine challenge, and a single-blind, placebo-controlled specific inhalation challenge with 0.1% manganese chloride solution. Clinical findings and laboratory test results remained normal but a significant bronchial hyperreactivity was found. During the specific inhalation challenge, dyspnea and a significant decrease in forced expiratory volume (FEV1) were observed. An increased proportion of eosinophils and basophils in induced sputum could also be noted at 4 and 24 h after the challenge. The argument for recognizing the condition as occupational asthma was a positive clinical response to the specific challenge test as well as the morphological changes found in induced sputum. To our knowledge, this is the first well-documented case of manganese-induced occupational asthma. PMID:18468975

Basidiomycetous and ascomycetous yeast species were tested for manganese tolerance. Basidiomycetous Cryptococcus humicola, Cryptococcus terricola, Cryptococcus curvatus and ascomycetous Candida maltosa, Kluyveromyces marxianus, Kuraishia capsulata, Lindnera fabianii and Sacharomyces cerevisiae were able to grow at manganese excess (2.5 mmol/L), while the growth of basidiomycetous Rhodotorula bogoriensis was completely suppressed. The lag phase duration increased and the exponential growth rate decreased at manganese excess. The increase of cell size and enlargement of vacuoles were characteristics for the cells grown at manganese excess. The alterations in inorganic polyphosphate content and cellular localization were studied. L. fabianii, K. capsulata, C. maltosa, and Cr. humicola accumulated the higher amounts of inorganic polyphosphates, while Cr. terricola and Cr. curvatus demonstrated no such accumulation. The polyphosphate content in the cell wall tested by DAPI staining increased in all species under the study; however, this effect was more pronounced in Cr. terricola and Cr. curvatus. The accumulation of Mg(2+) in the cell wall under Mn(2+) excess was observed in Cr. humicola, Cr. curvatus and Cr. terricola. The accumulation of polyphosphate and magnesium in the cell wall was supposed to be a factor of manganese tolerance in yeasts. PMID:26646947

The sorption of silver by poorly crystallized manganese oxides was studied using synthesized samples of three members of the manganous manganite (birnessite) group, of different chemical composition and crystallinity, and a poorly organized ??-MnO2. All four oxides sorbed significant quantities of silver. The manganous manganites showed the greatest sorption (up to 0.5 moles silver/mole MnOx at pH 7) while the ??-MnO2 showed the least (0.3 moles silver/ mole MnOx at pH 7). Sorption of silver was adequately described by the Langmuir equation over a considerable concentration range. The relationship failed at low pH values and high equilibrium silver concentrations. The sorption capacity showed a direct relationship with pH. However, the rate of increase of sorption capacity decreased at the higher pH values. Silver sorption maxima. were not directly related to surface area but appeared to vary with the amount of occluded sodium and potassium present in the manganese oxide. The important processes involved in the uptake of silver by the four poorly crystallized manganese oxides ara considered to be surface exchange for manganese, potassium and sodium as well as exchange for structural manganese, potassium and sodium. ?? 1973.

Seasonal manganese pollution has become an increasingly pressing water quality issue for water supply reservoirs in recent years. Manganese is a redox-sensitive element and is released from sediment under anoxic conditions near the sediment-water interface during summer and autumn, when water temperature stratification occurs. The reservoir water temperature and water dynamic conditions directly influence the formation of manganese pollution. Numerical models are useful tools to quantitatively evaluate manganese pollution and its influencing factors. This paper presents a reservoir manganese pollution model by adding a manganese biogeochemical module to a water quality model-CE-QUAL-W2. The model is applied to the Wangjuan reservoir (Qingdao, China), which experiences manganese pollution during summer and autumn. Field data are used to verify the model, and the results show that the model can reproduce the main features of the thermal stratification and manganese distribution. The model is used to evaluate the manganese pollution process and its four influencing factors, including air temperature, water level, wind speed, and wind directions, through different simulation scenarios. The results show that all four factors can influence manganese pollution. High air temperature, high water level, and low wind speed aggravate manganese pollution, while low air temperature, low water level, and high wind speed reduce manganese pollution. Wind that travels in the opposite direction of the flow aggravates manganese pollution, while wind in the same direction as the flow reduces manganese pollution. This study provides useful information to improve our understanding of seasonal manganese pollution in reservoirs, which is important for reservoir manganese pollution warnings and control. PMID:27068892

Manganese superoxide dismutase (MnSOD) is a nuclear-encoded antioxidant enzyme that localizes to the mitochondria. Expression of MnSOD is essential for the survival of aerobic life. Transgenic mice expressing a luciferase reporter gene under the control of the human MnSOD promoter demonstrate that the level of MnSOD is reduced prior to the formation of cancer. Overexpression of MnSOD in transgenic mice reduces the incidences and multiplicity of papillomas in a DMBA/TPA skin carcinogenesis model. However, MnSOD deficiency does not lead to enhanced tumorigenicity of skin tissue similarly treated because MnSOD can modulate both the p53-mediated apoptosis and AP-1-mediated cell proliferation pathways. Apoptosis is associated with an increase in mitochondrial levels of p53 suggesting a link between MnSOD deficiency and mitochondrial-mediated apoptosis. Activation of p53 is preventable by application of a SOD mimetic (MnTE-2-PyP5+). Thus, p53 translocation to mitochondria and subsequent inactivation of MnSOD explain the observed mitochondrial dysfunction that leads to transcription-dependent mechanisms of p53-induced apoptosis. Administration of MnTE-2-PyP5+ following apoptosis but prior to proliferation leads to suppression of protein carbonyls and reduces the activity of AP-1 and the level of the proliferating cellular nuclear antigen, without reducing the activity of p53 or DNA fragmentation following TPA treatment. Remarkably, the incidence and multiplicity of skin tumors are drastically reduced in mice that receive MnTE-2-PyP5+ prior to cell proliferation. The results demonstrate the role of MnSOD beyond its essential role for survival and suggest a novel strategy for an antioxidant approach to cancer intervention. PMID:20454814

Excessive manganese (Mn) uptake by brain cells, particularly in regions like the basal ganglia, can lead to toxicity. Mn2+ is transported into cells via a number of mechanisms, while Mn3+ is believed to be transported similarly to iron (Fe) via the transferrin (Tf) mechanism. Cellular Mn uptake is therefore determined by the activity of the mechanisms transporting Mn into each type of cell and by the amounts of Mn2+, Mn3+ and their complexes to which these cells are exposed; this complicates understanding the contributions of each transporter to Mn toxicity. While uptake of Fe3+ via the Tf mechanism is well understood, uptake of Mn3+ via this mechanism has not been systematically studied. The stability of the Mn3+Tf complex allowed us to form and purify this complex and label it with a fluorescent (Alexa green) tag. Using purified and labeled Mn3+Tf and biophysical tools, we have developed a novel approach to study Mn3+Tf transport independently of other Mn transport mechanisms. This approach was used to compare the uptake of Mn3+Tf into neuronal cell lines with published descriptions of Fe3+ uptake via the Tf mechanism, and to obtain quantitative information on Mn uptake via the Tf mechanism. Results confirm that in these cell lines significant Mn3+ is transported by the Tf mechanism similarly to Fe3+Tf transport; although Mn3+Tf transport is markedly slower than other Mn transport mechanisms. This novel approach may prove useful for studying Mn toxicity in other systems and cell types. PMID:23146871

Manganese (Mn) oxides are among the strongest sorbents and oxidants within the environment, controlling the fate and transport of numerous elements and the degradation of recalcitrant carbon. Both bacteria and fungi mediate the oxidation of Mn(II) to Mn(III/IV) oxides but the genetic and biochemical mechanisms responsible remain poorly understood. Furthermore, the physiological basis for microbial Mn(II) oxidation remains an enigma. We have recently reported that a common marine bacterium (Roseobacter sp. AzwK-3b) oxidizes Mn(II) via reaction with extracellular superoxide (O2-) produced during exponential growth. Here we expand this superoxide-mediated Mn(II) oxidation pathway to fungi, introducing a surprising homology between prokaryotic and eukaryotic metal redox processes. For instance, Stibella aciculosa, a common soil Ascomycete filamentous fungus, precipitates Mn oxides at the base of asexual reproductive structures (synnemata) used to support conidia (Figure 1). This distribution is a consequence of localized production of superoxide (and it's dismutation product hydrogen peroxide, H2O2), leading to abiotic oxidation of Mn(II) by superoxide. Disruption of NADPH oxidase activity using the oxidoreductase inhibitor DPI leads to diminished cell differentiation and subsequent Mn(II) oxidation inhibition. Addition of Cu(II) (an effective superoxide scavenger) leads to a concentration dependent decrease in Mn oxide formation. We predict that due to the widespread production of extracellular superoxide within the fungal and likely bacterial kingdoms, biological superoxide may be an important contributor to the cycling of Mn, as well as other metals (e.g., Hg, Fe). Current and future explorations of the genes and proteins involved in superoxide production and Mn(II) oxidation will ideally lend insight into the physiological and biochemical basis for these processes.

Oxygenic photosynthesis is the most important bioenergetic event in the history of our planet—it evolved once within the Cyanobacteria, and remained largely unchanged as it was transferred to algae and plants via endosymbiosis. Manganese plays a fundamental role in this history because it lends the critical redox behavior of the water-oxidizing complex of photosystem II. Constraints from the photoassembly of the Mn-bearing water-oxidizing complex fuel the hypothesis that Mn(II) once played a key role as an electron donor for anoxygenic photosynthesis prior to the evolution of oxygenic photosynthesis. Here we review the growing body of geological and geochemical evidence from the Archean and Paleoproterozoic sedimentary records that supports this idea and demonstrates that the oxidative branch of the Mn cycle switched on prior to the rise of oxygen. This Mn-oxidizing phototrophy hypothesis also receives support from the biological record of extant phototrophs, and can be made more explicit by leveraging constraints from structural biology and biochemistry of photosystem II in Cyanobacteria. These observations highlight that water-splitting in photosystem II evolved independently from a homodimeric ancestral type II reaction center capable of high potential photosynthesis and Mn(II) oxidation, which is required by the presence of homologous redox-active tyrosines in the modern heterodimer. The ancestral homodimer reaction center also evolved a C-terminal extension that sterically precluded standard phototrophic electron donors like cytochrome c, cupredoxins, or high-potential iron-sulfur proteins, and could only complete direct oxidation of small molecules like Mn2+, and ultimately water.

Sedimentary manganese deposits widely distribute in North Guangxi with the characteristic existing Celosia argentea. Celosia argentea is a kind of plant which has a strong ability to enrich manganese. In order to study the relationship between the hyperspectral characteristics of Celosia argentea and the concentration effect of manganese in the soil, we used soil of B layer in mining area, background soil and the soil adding reagent of MnCl4 to make up experimental sample soil with 10 levels Manganese content for the same batch Celosia argentea. The levels are 0mg/kg, 4500mg/kg, 9000mg/kg, 13500mg/kg, 18000mg/kg, 18020mg/kg, 18040mg/kg, 18080mg/kg, 18160mg/kg. ASD FieldSpec-4 has been used to measure the abnormal spectrums of these Celosia argentea through a whole growth cycle. After pretreating the spectral data, we used Successive Projections Algorithm (SPA) to extract the characteristic variables for extracting 1603 bands into 8 bands. Finally, the relationship between the spectral variables and the concentration of manganese was predicted by the Model of Partial Least Squares Regression (PLSR). The results show that the correlation coefficient-r2 are 0.8714 and 0.9141 in two sets of data. The prediction results are satisfactory, but the front 5 groups are closer to the regression line than the last 5 groups.

Manganese is an essential dietary nutrient and trace element with important roles in mammalian development, metabolism, and antioxidant defense. In healthy individuals, gastrointestinal absorption and hepatobiliary excretion are tightly regulated to maintain systemic manganese concentrations at physiologic levels. Interactions of manganese with other essential metals following high dose ingestion are incompletely understood. We previously reported that gavage manganese exposure in rats resulted in higher tissue manganese concentrations when compared with equivalent dietary or drinking water manganese exposures. In this study, we performed follow-up evaluations to determine whether oral manganese exposure perturbs iron, copper, or zinc tissue concentrations. Rats were exposed to a control diet with 10 ppm manganese or dietary, drinking water, or gavage exposure to approximately 11.1 mg manganese/kg body weight/day for 7 or 61 exposure days. While manganese exposure affected levels of all metals, particularly in the frontal cortex and liver, copper levels were most prominently affected. This result suggests an under-appreciated effect of manganese exposure on copper homeostasis which may contribute to our understanding of the pathophysiology of manganese toxicity. PMID:26988220

To determine the mechanism of manganese excretion from the liver into bile, manganese content in blood, bile, whole liver, and subcellular fractions of liver was measured following intraperitoneal injection of a single dose of manganese (49 mg Mn(OAc)/sub 2/. 4H/sub 2/O/kg body wt) in mice. Manganese in blood was rapidly incorporated into liver and appeared in bile within hours. Most of the absorbed manganese in liver was recovered in the mitochondrial-lysosomal fraction. Purified nuclei contained only one-tenth of the manganese found in the crude nuclear fraction. Sucrose density gradient centrifugation revealed that lysosomes took up and released manganese more rapidly than mitochondria. Also, manganese content in the liver and bile decreased following pretreatment with trypan blue. These values returned to normal with simultaneous administration of cortisone. Manganese released in vitro from the mitochondrial-lysosomal fraction and manganese in bile were measured as manganese acetate by gel filtration. The results suggest that liver lysosomes play an important role in intrahepatic movement and affect biliary excretion of absorbed manganese.

Sulfate reducing bacteria (SRB) are very potent MnO2 reducers by virtue of their sulfide production: H2S reacts rapidly with MnO2 to yield Mn(2), elemental sulfur, and water. In manganese rich zones, Mn cycles rapidly if sulfate is present to drive the reduction and the MnO2 precipitates and sinks into anaerobic zones. The production of sulfide (by organisms requiring organic carbon compounds) to reduce manganese oxides might act to couple the carbon and sulfur cycles in water bodies in which the two cycles are physically separated. Iron has been proposed for this provision of reducing power by (Jorgensen, 1983), but since MnS is soluble and FeS is very insoluble in water, it is equally likely that manganese rather than iron provides the electrons to the more oxidized surface layers.

The present work investigates the formation of manganese ferrite of nanosize by oxidation of MnO- and FeO-containing slag. A horizontal resistance furnace was used as an experimental setup. The experiment was conducted in the temperature range of 1573 K to 1673 K (1300 °C to 1400 °C) in an oxidizing atmosphere. The samples were quenched to the cold end of the furnace and were analyzed by X-ray diffraction (XRD). The XRD patterns of the products showed the presence of two phases—manganese ferrite and calcium silicate. The particle size of the manganese ferrite was estimated by the Scherrer formula to be in the range of nanometers.

The surface of Mars has long been considered a relatively oxidizing environment, an idea supported by the abundance of ferric iron phases observed there. However, compared to iron, manganese is sensitive only to high redox potential oxidants, and when concentrated in rocks, it provides a more specific redox indicator of aqueous environments. Observations from the ChemCam instrument on the Curiosity rover indicate abundances of manganese in and on some rock targets that are 1–2 orders of magnitude higher than previously observed on Mars, suggesting the presence of an as-yet unidentified manganese-rich phase. These results show that the Martian surface has at some point in time hosted much more highly oxidizing conditions than has previously been recognized.

A potable water treatment plant, designed to reduce manganese and iron in well water, experienced leaks in the 16 in. (406 mm) raw water headers about nine months after startup. The material, type 304 (UNS 30403) stainless steel, was purchased to American Society of Testing Materials specification A 778, with additional stipulations governing internal finish, the use of filler metal, and pickling for scale removal. Laboratory screenings of deposits for bacteria revealed some potentially additive corrosive effects from microbial action. However, the correlation of corrosion with the presence or absence of heat tint in the heat-affected zone of the circumferential welds prevailed as a primary cause of the corrosion observed beneath an adherent manganese-iron deposit in a low chloride, high manganese, raw water.

Synthetic manganese-activated calcites are shown to be practically inert to ultraviolet excitation in the range 2000-3500A, while they are luminescent under cathode-ray excitation. The incorporation of small amounts of an auxiliary impurity along with the manganese produces the strong response to ultraviolet radiation hitherto ascribed to CaCO3:Mn itself. Three such impurities have been studied: lead, thallium, and cerium. The first two induce excitation in the neighborhood of the mercury resonance line, while the cerium introduces a response principally to longer wave ultraviolet. The strong response to 2537A excitation shown by some natural calcites is likewise found to be due to the presence of lead along with the manganese, rather than to the manganese alone. The data do not warrant ascribing the longer wave-length ultraviolet-excited luminescence of all natural calcites to the action of an auxiliary impurity. The essential identity of the cathode-ray excited luminescence spectra of CaCO 3:Mn, CaCO3: (Pb+Mn), CaCO3:(Tl+Mn), and CaCO3:(Ce+Mn) with the 2537A-excited spectra of the latter three is evidence that the luminescent center in all cases is the manganese ion or the MnO6 group. It is shown that a "cascade" mechanism for the action of the auxiliary impurities, lead, thallium, and cerium, is incorrect; and that the phenomenon must be considered as a case of sensitized luminescence. Owing to the nature of cathode-ray excitation, the manganese activator can be excited by this agent even in the absence of a second impurity. For optical excitation, however, an absorption band for the ultraviolet must be established by building into the CaCO3:Mn a second impurity or "sensitizer.".

The role of the manganese (Mn) oxidation state on cellular Mn uptake and toxicity is not well understood. Therefore, undifferentiated PC12 cells were exposed to 0-200 {mu}M Mn(II)-chloride or Mn(III)-pyrophosphate for 24 h, after which cellular manganese levels were measured along with measures of cell viability, function, and cytotoxicity (trypan blue exclusion, medium lactate dehydrogenase (LDH), 8-isoprostanes, cellular ATP, dopamine, serotonin, H-ferritin, transferrin receptor (TfR), Mn-superoxide dismutase (MnSOD), and copper-zinc superoxide dismutase (CuZnSOD) protein levels). Exposures to Mn(III) >10 {mu}M produced 2- to 5-fold higher cellular manganese levels than equimolar exposures to Mn(II). Cell viability and ATP levels both decreased at the highest Mn(II) and Mn(III) exposures (150-200 {mu}M), while Mn(III) exposures produced increases in LDH activity at lower exposures ({>=}50 {mu}M) than did Mn(II) (200 {mu}M only). Mn(II) reduced cellular dopamine levels more than Mn(III), especially at the highest exposures (50% reduced at 200 {mu}M Mn(II)). In contrast, Mn(III) produced a >70% reduction in cellular serotonin at all exposures compared to Mn(II). Different cellular responses to Mn(II) exposures compared to Mn(III) were also observed for H-ferritin, TfR, and MnSOD protein levels. Notably, these differential effects of Mn(II) versus Mn(III) exposures on cellular toxicity could not simply be accounted for by the different cellular levels of manganese. These results suggest that the oxidation state of manganese exposures plays an important role in mediating manganese cytotoxicity.

Manganese dioxide was known two thousand years ago. It was described by Plinius. Later, Basilius Valentinus named it "Braunstein", the brownstone. Its chemical nature was recognized by Scheele and his student Gahn. Its first application in the field of batteries seems to have been by Ritter. Following Leclanchéś invention it has been used on a large scale in dry batteries. In 1977 about 300 000 metric tons of battery grade manganese dioxide were consumed. More than 50% of the oxide is derived from natural ores, and about one third is obtained as electrochemically deposited dioxide.

Several DOE sites have been contaminated by transuranicradionuclide (TRU) discharges including neptunium and plutonium. Theirinteraction with the surrounding geological media can affect thetransport and remediation of these radionuclides in the environment.Manganese based minerals, present as minor phases in the vadose zone, canpreferentially sequester TRU over other minerals present in largerquantities. The objective of this project is to understand theinteractions between plutonium and neptunium and manganese oxyhydroxideminerals to predict potential hazards they represent to the environment,as well as to provide important scientific information for the design ofeffective remediation strategies for contaminated DOE sites.

REACT Project: PNNL is working to reduce the cost of wind turbines and EVs by developing a manganese-based nano-composite magnet that could serve as an inexpensive alternative to rare-earth-based magnets. The manganese composite, made from low-cost and abundant materials, could exceed the performance of today’s most powerful commercial magnets at temperature higher than 200°C. Members of PNNL’s research team will leverage comprehensive computer high-performance supercomputer modeling and materials testing to meet this objective. Manganese-based magnets could withstand higher temperatures than their rare earth predecessors and potentially reduce the need for any expensive, bulky engine cooling systems for the motor and generator. This would further contribute to cost savings for both EVs and wind turbines.

Manganese is an essential trace element that is required for the activity of several enzymes. Manganese is also quite toxic when ingested in large amounts, such as the inhalation of Mn-laden dust by miners. This review examines Mn intake by way of the food supply and poses the question: Is there reason to be concerned with Mn toxicity or deficiency in free-living populations in North America? Although much remains to be learned of the functions of Mn, at present there are only a few vaguely described cases of Mn deficiency in the medical literature. Given the heterogeneity of the North American food supply, it is difficult to see the possibility of more than greatly isolated and unique instances of Mn deficiency. However, low Mn-dependent superoxide dismutase activity may be associated with cancer susceptibility, and deserves further study. There may be reasons, however, to be concerned about Mn toxicity under some very specialized conditions. Increasing numbers of young people are adopting a vegetarian lifestyle which may greatly increase Mn intake. Iron deficiency may increase Mn absorption and further increase the body-burden of Mn, especially in vegetarians. Mn is eliminated primarily through the bile, and hepatic dysfunction could depress Mn excretion and further contribute to the body burden. Would such a combination of events predispose substantial numbers of people to chronic Mn toxicity? At present, there is no definite proof of this occurring, but given the state of knowledge at the present time, more studies with longer time-frames and more sensitive methods of analysis are needed. PMID:10475586

Manganese oxide minerals are a significant component of the fracture lining mineralogy at Yucca Mountain (Carlos et al., 1993) and within the tuff-confining unit at Yucca Flat (Prothro, 1998), Pahute Mesa (Drellack et al., 1997), and other locations at the Nevada Test Site (NTS). Radionuclide sorption to manganese oxide minerals was not included in recent Lawrence Livermore National Laboratory (LLNL) hydrologic source term (HST) models which attempt to predict the migration behavior of radionuclides away from underground nuclear tests. However, experiments performed for the Yucca Mountain Program suggest that these minerals may control much of the retardation of certain radionuclides, particularly Np and Pu (Triay et al., 1991; Duff et al., 1999). As a result, recent HST model results may significantly overpredict radionuclide transport away from underground nuclear tests. The sorption model used in HST calculations performed at LLNL includes sorption to iron oxide, calcite, zeolite, smectite, and mica minerals (Zavarin and Bruton 2004a; 2004b). For the majority of radiologic source term (RST) radionuclides, we believe that this accounts for the dominant sorption processes controlling transport. However, for the case of Np, sorption is rather weak to all but the iron and manganese oxides (Figure 1). Thus, we can expect to significantly reduce predicted Np transport by accounting for Np sorption to manganese oxides. Similarly, Pu has been shown to be predominantly associated with manganese oxides in Yucca Mountain fractured tuffs (Duff et al., 1999). Recent results on colloid-facilitated Pu transport (Kersting and Reimus, 2003) also suggest that manganese oxide coatings on fracture surfaces may compete with colloids for Pu, thus reducing the effects of colloid-facilitated Pu transport (Figure 1b). The available data suggest that it is important to incorporate Np and Pu sorption to manganese oxides in reactive transport models. However, few data are available for

The impact of additional Pt and Ni monosilicide (NiSi) crystal orientation on channel stress from Ni silicide in metal-oxide-semiconductor field-effect transistors (MOSFETs) has been demonstrated. The channel stress generation mechanism can be explained by the NiSi crystal orientation. In pure Ni silicide films, the channel stress in the p-type substrate is much larger than that in the n-type one, since the NiSi a-axis parallel to the channel direction is strongly aligned on the p-type substrate compared with on the n-type one. On the other hand, in NiPt silicide films, the difference in the channel stress between the p- and n-type substrates is small, because the NiSi crystal orientation on the p-type substrate is similar to that on the n-type one. These results can be explained by the Pt segregation at the interface between the NiSi film and the Si surface. Segregated Pt atoms cause the NiSi b-axis to align normal to the Si(001) surface in the nucleation step owing to the expansion of the NiSi lattice spacing at the NiSi/Si interface. Furthermore, the Pt segregation mechanism is considered to be caused by the grain boundary diffusion in the Ni2Si film during NiSi formation. We confirmed that the grains of Ni2Si on the p-type substrate are smaller than those on the n-type one. The Ni2Si film on the p-type substrate has more grain boundary diffusion paths than that on the n-type one. Therefore, the amount of Pt segregation at the NiSi/Si interface on the p-type substrate is larger than that on the n-type one. Consequently, the number of NiSi grains with the b-axis aligned normal to the Si(001) in the p-type substrate is larger than that in the n-type one. As a result, the channel stress induced by NiPt silicide in PMOS is larger than that in NMOS. According to this mechanism, controlling the Pt concentration at the NiSi/Si interface is one of the key factors for channel stress engineering.

Conference Summary Manganese (Mn) is a well established neurotoxin associated with specific damage to the basal ganglia in humans. The phenotype associated with Mn neurotoxicity was first described in two workers with occupational exposure to Mn oxide.(Couper, 1837) Although the description did not use modern clinical terminology, a parkinsonian illness characterized by slowness of movement (bradykinesia), masked facies, and gait impairment (postural instability) appears to have predominated. Nearly 100 years later an outbreak of an atypical parkinsonian illness in a Chilean Mn mine provided a phenotypic description of a fulminant neurologic disorder with parkinsonism, dystonia, and neuropsychiatric symptoms.(Rodier J, 1955) Exposures associated with this syndrome were massive and an order of magnitude greater than modern exposures.(Rodier J, 1955; Hobson et al., 2011) The clinical syndrome associated with Mn neurotoxicity has been called manganism. Modern exposures to Mn occur primarily through occupations in the steel industry and welding. These exposures are often chronic and varied, occurring over decades in the healthy workforce. Although the severe neurologic disorder described by Rodier and Couper are no longer seen, several reports have suggested a possible increased risk of neurotoxicity in these workers.(Racette et al., 2005b; Bowler et al., 2007; Harris et al., 2011) Based upon limited prior imaging and pathologic investigations into the pathophysiology of neurotoxicity in Mn exposed workers,(Huang et al., 2003) many investigators have concluded that the syndrome spares the dopamine system distinguishing manganism from Parkinson disease (PD), the most common cause of parkinsonism in the general population, and a disease with characteristic degenerative changes in the dopaminergic system.(Jankovic, 2005) The purpose of this symposium was to highlight recent advances in the understanding of the pathophysiology of Mn associated neurotoxicity from C. elegans

Silicon is an important candidate for the light element in the outer core. Here we present new measurements of the equation-of-state, thermal expansion, melting temperature, and thermal conductivity of iron silicide (Fe5Si3) at high pressures and temperatures. We performed a series of X-ray diffraction experiments in the laser-heated diamond anvil cell on Fe5Si3 at ALS beamline 12.2.2. Diffraction patterns and temperature-versus-laser power curves were measured in situ at pressures up to 58 GPa and temperatures up to 2300 K. In one set of experiments both NaCl and Ne were used as the pressure transmitting, thermal insulator and pressure calibrant. In a second set of experiments, only NaCl was present and served those three purposes. The measurements yield a new thermoelastic equation of state for Fe5Si3, including bulk modulus, high-pressure thermal expansion, and the Grüneisen parameter. In addition, we have determined a lower bound on the melting behavior up to 58 GPa. This information helps constrain compositionally-sensitive models describing the density, compressibility, and dynamics of Earth's core. The temperature-versus-laser power measurements provide information about the heat flow environment in the diamond anvil cell. A comparison of the temperature-versus-laser power measurements for pure iron and Fe5Si3 yields a measure of how the presence of Si influences the thermal conductivity of iron at high pressures and temperatures. Our measurements also show a jump in thermal conductivity of NaCl across the B1- B2 phase transition. This information is important for interpreting thermal conductivity values in the present work and also has broader implications for experimental design and data interpretation in laser-heated diamond anvil cell experiments.

Objective We reviewed the scientific background for the current health-based World Health Organization (WHO) guideline value for manganese in drinking water. Data sources and extraction The initial starting point was the background document for the development of the WHO’s guideline value for manganese in drinking water as well as other regulations and recommendations on manganese intake levels. Data referred to in these documents were traced back to the original research papers. In addition, we searched for scientific reports on manganese exposure and health effects. Data synthesis The current health-based guideline value for manganese in drinking water is based partly on debatable assumptions, where information from previous reports has been used without revisiting original scientific articles. Presently, preparation of common infant formulas with water containing manganese concentrations equivalent to the WHO guideline value will result in exceeding the maximum manganese concentration for infant formula. However, there are uncertainties about how this maximum value was derived. Concurrently, there is increasing evidence of negative neurologic effects in children from excessive manganese exposure. Conclusions The increasing number of studies reporting associations between neurologic symptoms and manganese exposure in infants and children, in combination with the questionable scientific background data used in setting the manganese guideline value for drinking water, certainly warrant a re-evaluation of the guideline value. Further research is needed to understand the causal relationship between manganese exposure and children’s health, and to enable an improved risk assessment. PMID:18007980

Extended X-ray Absorption Fine Structure (EXAFS) studies on the manganese contained in spinach chloroplasts and on certain di-u-oxo bridged manganese dimers of the form (X{sub 2}Mn)O{sub 2}(MnX{sub 2} (X=2,2'-bypyridine and 1,10-phenanthroline) are reported. From these studies, the manganese associated with photosynthetic oxygen evolution is suggested to occur as a bridged transition metal dimer with most likely another manganese. Extensive details on the analysis are included.

Cornstalk is usually directly used as a reductant in reductive leaching manganese. However, low utilization of cornstalk makes low manganese dissolution ratio. In the research, pretreatment for cornstalk was proposed to improve manganese dissolution ratio. Cornstalk was preprocessed by a heated sulfuric acid solution (1.2 M of sulfuric acid concentration) for 10 min at 80°C. Thereafter, both the pretreated solution and the residue were used as a reductant for manganese leaching. This method not only exhibited superior activity for hydrolyzing cornstalk but also enhanced manganese dissolution. These effects were attributed to an increase in the amount of reductive sugars resulting from lignin hydrolysis. Through acid pretreatment for cornstalk, the manganese dissolution ratio was improved from 50.14% to 83.46%. The present work demonstrates for the first time the effective acid pretreatment of cornstalk to provide a cost-effective reductant for manganese leaching.

The ability of oral Mn(+2) to produce the depletions of dopamine in the corpus striata characteristic of the Parkinson-like syndrome in manganese workers was examined in rats. A second objective of this work was to study the biological interactions between Mn(+2) and sodium hexam...

Manganese (Mn), a nutrient required for normal metabolic function, is also a persistent air pollutant and a known neurotoxin at high concentrations. Elevated exposures can result in a number of motor and cognitive deficits. Quantifying chronic personal exposures in residential po...

Manganese (Mn) is an essential element with natural low levels found in water, food, and air, but due to industrialized processes, both workplace and the environmental exposures to Mn have increased. Recently, environmental studies have reported physical and mental health problem...

Research was performed using manganese dioxide (MnO2) to demonstrate that above pH3 cations are adsorbed from solution in the order of their affinity, and that the interaction is characterized by the pH dependence of the metal. The relationship of the zero point charge of pH and ...

The neurotoxicity of manganese (Mn) is well established, yet the risk assessment of Mn is made complex by certain enigmas. These include apparently greatertoxicity via inhalation compared to oral exposure and greater toxicity in humans compared to rats. In addition, until recentl...

Although manganese (Mn) is an essential nutrient, occupational studies have shown inhaling high levels of Mn can lead to adverse nervous system health effects. Few studies have examined the health effects of air-Mn exposure on adults in a community. We conducted a cross-sectional...

A recent discovery of manganese oxides in Martian rocks might tell us that the Red Planet was once more Earth-like than previously believed. So what exactly does that mean? Nina Lanza, Los Alamos scientist and lead author of the new paper about these findings in Geophysical Research Letters, breaks it down for us.

Investigators expect to study the mechanisms by which manganese enters and leaves the brain across the blood–brain barrier and, in particular, whether transporter molecules are involved. The investigators plan to use in vivo brain perfusion in rats as well as in vitro...

Using data obtained in recent years, we considered the external mass balance and characteristics of internal iron and manganese cycles in Lake Baikal (biological uptake, remineralization, sedimentary and diffusive fluxes, accumulation in sediments, time of renewal, etc.). Some previous results and common concepts were critically reevaluated. ?? Pleiades Publishing, Ltd. 2007.

Four male and four female rhesus monkeys were exposed to manganese oxide (Mn3O4) aerosol at 100 micrograms/cubic meter in an exposure chamber for periods up to 66 weeks. Three male and three female monkeys were maintained as unexposed controls. Observation and clinical chemistry ...

Background: The towns of Marietta and East Liverpool (EL), Ohio, have been identified as having elevated manganese (Mn) in air due to industrial pollution. Objectives: To evaluate relationships between environmental Mn (Mn-air) exposure and distance from the source and cognitive...

... published at 63 FR 30599, June 5, 1998, and may be downloaded from the Commission's World Wide Web site at... reviews pursuant to section 751(c)(5) of the Act should proceed (64 FR 46407, August 25, 1999). A record... COMMISSION Electrolytic Manganese Dioxide From Greece and Japan AGENCY: United States International...

..., including the text of subpart F of part 207, are published at 63 FR 30599, June 5, 1998, and may be... interested party group response to its notice of institution (64 FR 23675, Mar. 3, 1999) was adequate with... COMMISSION Electrolytic Manganese Dioxide from Greece and Japan AGENCY: United States International...

The patient's family bought a home in a suburb, but the proximity of the house to wetlands and its distance from the town water main prohibited connecting the house to town water. The family had a well drilled and they drank the well water for 5 years, despite the fact that the water was turbid, had a metallic taste, and left an orange-brown residue on clothes, dishes, and appliances. When the water was tested after 5 years of residential use, the manganese concentration was elevated (1.21 ppm; U.S. Environmental Protection Agency reference, < 0.05 ppm). The family's 10-year-old son had elevated manganese concentrations in whole blood, urine, and hair. The blood manganese level of his brother was normal, but his hair manganese level was elevated. The patient, the 10-year-old, was in the fifth grade and had no history of learning problems; however, teachers had noticed his inattentiveness and lack of focus in the classroom. Our results of cognitive testing were normal, but tests of memory revealed a markedly below-average performance: the patient's general memory index was at the 13th percentile, his verbal memory at the 19th percentile, his visual memory at the 14th percentile, and his learning index at the 19th percentile. The patient's free recall and cued recall tests were all 0.5-1.5 standard deviations (1 SD = 16th percentile) below normal. Psychometric testing scores showed normal IQ but unexpectedly poor verbal and visual memory. These findings are consistent with the known toxic effects of manganese, although a causal relationship cannot necessarily be inferred. PMID:12055054

The primary major deposit of manganese in the US which can be readily mined by an in situ process is located in the Emily district of Minnesota. The US Bureau of Mines Research Centers at both the Twin Cities and Salt Lake City have developed a process for extracting and refining manganese in the form of a high-purity carbonate product. This product has been formulated into pellets by a multi-step process of drying, calcination, and induration to produce relatively high-strength formulations which are capable of being used for hot fuel gas desulfurization. These pellets, which have been developed at the University of Minnesota under joint sponsorship of the US Department of Energy and the US Bureau of Mines, appear superior to other, more expensive, formulations of zinc titanate and zinc ferrite which have previously been studied for multi-cycle loading (desulfurization) and regeneration (evolution of high-strength SO{sub 2} and restoration of pellet reactivity). Although these other formulations have been under development for the past twelve years, their prices still exceed $7 per pound. If manganese pellets perform as predicted in fixed bed testing, and if a significant number of utilities which burn high-sulfur coals incorporate combined-cycle gasification with hot coal gas desulfurization as a viable means of increasing conversion efficiencies, then the potential market for manganese pellets may be as high as 200,000 tons per year at a price not less than $3 per pound. This paper discusses the role of manganese pellets in the desulfurization process with respect to the integrated gasification combined-cycle (IGCC) for power generation.

In this article we present the results of Cr isotope investigations of different types of carbonaceous chondrites and of the pallasite Eagle Station. The 53Cr/ 52Cr ratios in the bulk samples of carbonaceous chondrites are correlated with 55Mn/ 52Cr ratios. The slope of the correlation line yields a 53Mn/ 55Mn ratio of (8.5 ± 1.5) × 10 - 6 at the time of Mn/Cr fractionation. Mapping this ratio onto an absolute time scale yields a time for this event of 4568.1 + 0.8/- 1.1 Ma ago. This time is very similar to the formation age of Efremovka CAIs of 4567.2 ± 0.6 Ma [Y. Amelin, A. N. Krot, I. D. Hutcheon, A. A. Ulyanov, Lead isotopic ages of chondrules and calcium-aluminum-rich inclusions, Science 297 (2002) 1678-1683], to a time of the chondrule formation of 4568 ± 1 Ma ago [L.E. Nyquist, D. Lindstrom, D. Mittlefehldt, C.-Y. Shih, H. Wiesmann, S. Wentworth, R. Martinez, Manganese-chromium formation intervals for chondrules from the Bishunpur and Chainpur meteorites, Meteorit. Planet. Sci. 36 (2001) 911-938], which, most likely, constrains early global high-temperature Mn/Cr fractionation in a nebular setting. The bulk samples of carbonaceous chondrites exhibit clear 54Cr excesses ( 54Cr *) that are correlated with the 53Cr excesses ( 53Cr *) and also with Mn/Cr ratios. One possible explanation of this correlation is that 54Cr * is also radiogenic, like 53Cr *, and was formed by the decay of the short-lived parent radionuclide 54Mn. The very short half-life of 54Mn of 312 days would require that both short-lived radionuclides 53Mn and 54Mn were generated locally in spallation reactions during the early period of an active sun. The alternative and possibly more plausible explanation is the heterogeneous addition of presolar material. The presolar component, enriched in 54Cr, is mostly contained in the matrix of carbonaceous chondrites. The relative amount of matrix decreases in the sequence CI > CM > CO,CV. A large proportion of Mn is associated with the matrix while

The possible roles of siderophores (high affinity chelators of iron(III)) in the biogeochemistry of manganese remain unknown. Here we investigate the interaction of Mn(III) with a pyoverdine-type siderophore (PVD MnB1) produced by the model Mn(II)-oxidizing bacterium Pseudomonas putida strain MnB1. PVD MnB1 confirmed typical pyoverdine behavior with respect to: (a) its absorption spectrum at 350-600 nm, both in the absence and presence of Fe(III), (b) the quenching of its fluorescence by Fe(III), (c) the formation of a 1:1 complex with Fe(III), and (d) the thermodynamic stability constant of its Fe(III) complex. The Mn(III) complex of PVD MnB1 had a 1:1 Mn:pvd molar ratio, showed fluorescence quenching, and exhibited a light absorption spectrum (A max = 408-410 nm) different from that of either PVD MnB1-Fe(III) or uncomplexed PVD MnB1. Mn(III) competed strongly with Fe(III) for binding by PVD MnB1 in culture filtrates (pH 8, 4°C). Equilibration with citrate, a metal-binding ligand, did not detectably release Mn from its PVD MnB1 complex at a citrate/PVD MnB1 molar ratio of 830 (pH 8, 4°C), whereas pyrophosphate under the same conditions removed 55% of the Mn from its PVD MnB1 complex. Most of the PVD MnB1-complexed Mn was released by reaction with ascorbate, a reducing agent, or with EDTA, a ligand that is also oxidized by Mn(III). Data on the competition for binding to PVD MnB1 by Fe(III) vs. Mn(III) were used to determine a thermodynamic stability constant (nominally at 4°C) for the neutral species MnHPVD MnB1 (log K = 47.5 ± 0.5, infinite dilution reference state). This value was larger than that determined for FeHPVD MnB1 (log K = 44.6 ± 0.5). This result has important implications for the metabolism, solubility, speciation, and redox cycling of manganese, as well as for the biologic uptake of iron.

Nano-structured silicon anodes are attractive alternatives to graphitic carbons in rechargeable Li-ion batteries, owing to their extremely high capacities. Despite their advantages, numerous issues remain to be addressed, the most basic being to understand the complex kinetics and thermodynamics that control the reactions and structural rearrangements. Elucidating this necessitates real-time in situ metrologies, which are highly challenging, if the whole electrode structure is studied at an atomistic level for multiple cycles under realistic cycling conditions. Here we report that Si nanowires grown on a conducting carbon-fibre support provide a robust model battery system that can be studied by (7)Li in situ NMR spectroscopy. The method allows the (de)alloying reactions of the amorphous silicides to be followed in the 2nd cycle and beyond. In combination with density-functional theory calculations, the results provide insight into the amorphous and amorphous-to-crystalline lithium-silicide transformations, particularly those at low voltages, which are highly relevant to practical cycling strategies. PMID:24488002

This presentation will review recent measurement results of thermoelectric properties of individual bismuth telluride nanoplates, semiconductor nanowires, and silicide nanocomposites. In experiments with these realistic nanostructured materials, a number of factors influence the transport properties. For example, unintentional doping, interface roughness and impurities can often obscure the predicted effects of the low-dimensional electronic density of states and the protected surface states, the latter of which have been suggested for bismuth telluride and other thermoelectric materials, now also referred as topological insulators. Similarly, impurities and defects as well as contact thermal resistance can play an important role in phonon transport in nanostructures, making it nontrivial to quantify the actual effects of phonon-surface scattering and other intriguing low-dimensional phonon transport phenomena. Because of these experimental complications, diverse theoretical interpretations of experimental results have appeared in the literature, and will be discussed. Moreover, the effects of twin defects and crystal complexity on thermoelectric transport in nanostructures will be examined based on measurement results of III-V and silicide nanostructures.

Evaluation of the practical significance of manganese-iron interactions has been hampered by the limited methodologies available to assess manganese status. Manganese status has not been monitored longitudinally in control studies with humans. Forty-eight women were recruited for a double blind 125-day supplementation study. After an initial 5-day baseline period, subjects were assigned to one of four treatments: placebo; 30 mg iron as ferrous fumarate daily; 15 mg manganese as an amino acid chelated manganese supplement daily or both the iron and manganese supplements daily. Dietary information, blood and 3-day urine samples were collected during the baseline period and after 20, 55, 85 and 120 days of consuming the supplements. Urinary manganese excretion ranged from 0.11 to 1.40 {mu}g/day. Serum manganese ranged from 0.16 to 1.92 {mu}g/l. Serum was also analyzed for iron, zinc, copper, ferritin and transferrin concentrations. Lymphocytes were isolated and manganese-dependent superoxide dismutase activity was determined as a new method to assess manganese status. Plasma cholesterol ranged from 126 to 229 mg/dl and HDL cholesterol ranged from 31 to 84 mg/dl. Plasma triglycerides were determined and LDL cholesterol was calculated by difference.

Depth profiles of metals in Lake Vanda, a permanently ice-covered, stratified Antarctic lake, suggest the importance of particulate manganese oxides in the scavenging, transport, and release of metals. Since manganese oxides can be solubilized by manganese-reducing bacteria, microbially mediated manganese reduction was investigated in Lake Vanda. Microbes concentrated from oxic regions of the water column, encompassing a peak of soluble manganese [Mn(II)], reduced synthetic manganese oxides (MnO{sub 2}) when incubated aerobically, Pure cultures of manganese-reducing bacteria were readily isolated from waters collected near the oxic Mn(II) peak. Based on phylogenetic analysis of the 16S rRNA gene sequence, most of the isolated manganese reducers belong to the genus Carnobacterium. Cultures of a phylogenetically representative strain of Carnobacterium reduced synthetic MnO{sub 2} in the presence of sodium azide, as was seen in field assays. Unlike anaerobes that utilize manganese oxides as terminal electron acceptors in respiration, isolates of the genus Carnobacterium reduced Mn(IV) via a diffusible compound under oxic conditions. The release of adsorbed trace metals accompanying the solubilization of manganese oxides may provide populations of Carnobacterium with a source of nutrients in this extremely oligotrophic environment.

Depth profiles of metals in Lake Vanda, a permanently ice-covered, stratified Antarctic lake, suggest the importance of particulate manganese oxides in the scavenging, transport, and release of metals. Since manganese oxides can be solubilized by manganese-reducing bacteria, microbially mediated manganese reduction was investigated in Lake Vanda. Microbes concentrated from oxic regions of the water column, encompassing a peak of soluble manganese [Mn(II)], reduced synthetic manganese oxides (MnO2) when incubated aerobically. Pure cultures of manganese-reducing bacteria were readily isolated from waters collected near the oxic Mn(II) peak. Based on phylogenetic analysis of the 16S rRNA gene sequence, most of the isolated manganese reducers belong to the genus Carnobacterium. Cultures of a phylogenetically representative strain of Carnobacterium reduced synthetic MnO2 in the presence of sodium azide, as was seen in field assays. Unlike anaerobes that utilize manganese oxides as terminal electron acceptors in respiration, isolates of the genus Carnobacterium reduced Mn(IV) via a diffusible compound under oxic conditions. The release of adsorbed trace metals accompanying the solubilization of manganese oxides may provide populations of Carnobacterium with a source of nutrients in this extremely oligotrophic environment. PMID:9758801

The efficiency of manganese removal in conventional groundwater treatment consisting of aeration followed by rapid sand filtration, strongly depends on the ability of filter media to promote auto-catalytic adsorption of dissolved manganese and its subsequent oxidation. Earlier studies have shown that the compound responsible for the auto-catalytic activity in ripened filters is a manganese oxide called Birnessite. The aim of this study was to determine if the ripening of manganese removal filters and the formation of Birnessite on virgin sand is initiated biologically or physico-chemically. The ripening of virgin filter media in a pilot filter column fed by pre-treated manganese containing groundwater was studied for approximately 600 days. Samples of filter media were taken at regular time intervals, and the manganese oxides formed in the coating were analysed by Raman spectroscopy, Electron Paramagnetic Resonance (EPR) and Scanning Electron Microscopy (SEM). From the EPR analyses, it was established that the formation of Birnessite was most likely initiated via biological activity. With the progress of filter ripening and development of the coating, Birnessite formation became predominantly physico-chemical, although biological manganese oxidation continued to contribute to the overall manganese removal. The knowledge that manganese removal in conventional groundwater treatment is initiated biologically could be of help in reducing typically long ripening times by creating conditions that are favourable for the growth of manganese oxidizing bacteria. PMID:25463936

Manganese (Mn) is an essential trace element, but excess exposure leads to accumulation in biological tissues, including the brain. Chronically high Mn levels in the brain are neurotoxic and can result in a progressive, irreversible neurological disorder known as manganism. Manganism has signs and symptoms similar to, but distinguishable from idiopathic Parkinson’s disease, which include both psychological and motor disturbances. Evidence suggests that Mn exposure impacts neurotransmitter levels in the brain. However, it remains unclear if subacute, low-level Mn exposure resulted in alterations in neurotransmitter systems with concomitant behavioral deficits. The current study used high performance liquid chromatography to quantify neurotransmitter levels in rat striatum (STR), substantia nigra (SN), and hippocampus (HP). Subacute Mn exposure via i.p. injection of 15 mg Mn/kg as MnCl2 caused significantly increased dopamine (DA) levels in the STR. The enhancement was accompanied by significantly elevated levels of the DA metabolites, 3,4-dihydroxyphenylacetic acid (DOPAC) and homovanillic acid (HVA), in the STR. In addition, levels of HVA were significantly increased in the SN and HP. These data indicate that subacute, low-level Mn exposure disrupts multiple neurotransmitter systems in the rat brain which may be responsible, in part, for observed locomotor deficits. PMID:25117542

This study pioneered an approach that determined the effects of excess manganese (Mn) on three species; Datura stramonium, Alhagi camelthorn and Chenopodium ambrosioides. We investigated their levels of Mn, antioxidative enzymes and oxidative damage biomarkers in plants (zone 1) in and outside (zone 2) the Mn mine. The results showed that total and available Mn were at toxic levels for plants growing on zone 1. The Mn levels in each plant species were higher in leaves, stems and roots. Mn was only accumulated significantly in leaf vacuoles of A. camelthorn. Antioxidative enzyme activities of C. ambrosioides and/or D. stramonium in zone 1 were higher in leaves, stems and then in their roots. Malondialdehyde (MDA) and dityrosine levels were insignificantly higher in tissues of the studied plants in zone 1 with respect to zone 2. The roots of studied plants showed significantly higher levels of these biomarkers in comparison with their leaves in zone 1. Accordingly, antioxidative enzymatic response to Mn-stress in D. stramonium and C. ambrosioides and possibly accumulation of Mn in leaf vacuoles of A. camelthorn, protected them from oxidative damages and involved in their tolerance in Mn mine. PMID:18068229

The main route to manganese (Mn) excretion is in the bile, which normally begins within the first few days of life. The objective of the research was: to determine when Mn excretion commences; to determine the Mn content in liver, heart, kidney and brain of baby pigs born to sows on a high or low Mn diet; and compare these values with sow milk concentration. The Mn concentration in sow milk increases from day 1 to day 3 to day 7 and was consistently higher in the high Mn group vs the low Mn group. Initial excretions of Mn were high at birth and gradually decreased by day 4, then increased slightly on day 7. The Mn excretion values were also consistently higher in the high Mn group vs the low Mn group. There were no significant differences between Mn values in any of the organs from baby pigs in the low or high Mn groups. In both groups there was a significant increase in organ Mn concentration between day of birth and day 7. Thus, baby pigs consuming sow milk of high or low Mn concentrations accumulated the amount of Mn needed for growth and tended to excrete any excess.

Manganese homeostasis involves coordinated regulation of specific proteins involved in manganese influx and efflux. However, the proteins that are involved in detoxification/efflux have not been completely resolved nor has the basis by which they select their metal substrate. Here, we compared six proteins, which were reported to be involved in manganese detoxification/efflux, by evaluating their ability to reduce manganese toxicity in chicken DT40 cells, finding that human ZnT10 (hZnT10) was the most significant contributor. A domain swapping and substitution analysis between hZnT10 and the zinc-specific transporter hZnT1 showed that residue Asn(43), which corresponds to the His residue constituting the potential intramembranous zinc coordination site in other ZnT transporters, is necessary to impart hZnT10's unique manganese mobilization activity; residues Cys(52) and Leu(242) in transmembrane domains II and V play a subtler role in controlling the metal specificity of hZnT10. Interestingly, the His → Asn reversion mutant in hZnT1 conferred manganese transport activity and loss of zinc transport activity. These results provide important information about manganese detoxification/efflux mechanisms in vertebrate cells as well as the molecular characterization of hZnT10 as a manganese transporter. PMID:27226609

This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites

We investigated the electrical properties and derived the energy band structures of amorphous Si-rich W silicide (a-WSi{sub n}) films and approximately 1-nm-thick crystalline WSi{sub n} epitaxial films (e-WSi{sub n}) on Si (100) substrates with composition n = 8–10, both composed of Si{sub n} clusters each of which encapsulates a W atom (WSi{sub n} clusters). The effect of annealing in the temperature range of 300–500 °C was also investigated. The Hall measurements at room temperature revealed that a-WSi{sub n} is a nearly intrinsic semiconductor, whereas e-WSi{sub n} is an n-type semiconductor with electron mobility of ∼8 cm{sup 2}/V s and high sheet electron density of ∼7 × 10{sup 12 }cm{sup −2}. According to the temperature dependence of the electrical properties, a-WSi{sub n} has a mobility gap of ∼0.1 eV and mid gap states in the region of 10{sup 19 }cm{sup −3} eV{sup −1} in an optical gap of ∼0.6 eV with considerable band tail states; e-WSi{sub n} has a donor level of ∼0.1 eV with sheet density in the region of 10{sup 12 }cm{sup −2} in a band gap of ∼0.3 eV. These semiconducting band structures are primarily attributed to the open band-gap properties of the constituting WSi{sub n} cluster. In a-WSi{sub n}, the random network of the clusters generates the band tail states, and the formation of Si dangling bonds results in the generation of mid gap states; in e-WSi{sub n}, the original cluster structure is highly distorted to accommodate the Si lattice, resulting in the formation of intrinsic defects responsible for the donor level.

Nickel based alloys of the type Hastelloy-N™ are ideal candidate materials for molten salt reactors, as well as for applications such as pressure vessels, due to their excellent resistance to creep, oxidation and corrosion. In this work, the authors have attempted to understand the effects of welding on the morphology, chemistry and crystal structure of the precipitates in the heat affected zone (HAZ) and the weld zone of a Ni–Cr–Mo–Fe–Si alloy similar to Hastelloy-N™ in composition, by using characterization techniques such as scanning and transmission electron microscopy. Two plates of a Ni–Cr–Mo–Fe–Si alloy GH-3535 were welded together using a TiG welding process without filler material to achieve a joint with a curved molten zone with dendritic structure. It is evident that the primary precipitates have melted in the HAZ and re-solidified in a eutectic-like morphology, with a chemistry and crystal structure only slightly different from the pre-existing precipitates, while the surrounding matrix grains remained unmelted, except for the zones immediately adjacent to the precipitates. In the molten zone, the primary precipitates were fully melted and dissolved in the matrix, and there was enrichment of Mo and Si in the dendrite boundaries after solidification, and re-precipitation of the complex carbides/silicides at some grain boundaries and triple points. The nature of the precipitates in the molten zone varied according to the local chemical composition. - Graphical abstract: Display Omitted - Highlights: • Ni-based alloy with Cr, Mo, Si, Fe and C was welded, examined with SEM, EBSD, and TEM. • Original Ni{sub 2}(Mo,Cr){sub 4}(Si,C) carbides changed from equiaxed to lamellar shape in HAZ. • Composition and crystal structure remained almost unchanged in HAZ. • Original carbides changed to lamellar Ni{sub 3}(Mo,Cr){sub 3}(Si,C) in some cases in weld metal. • Precipitates were mostly incoherent, but semi-coherent in some cases in weld

An organic manganese compound is currently added to gasoline to replace tetraethyl lead as an antiknock fuel additive in the U.S. and Canada. Combustion exhaust gases contain manganese oxides. Manganese oxides are known to cause various deleterious health effects in experimental animals and humans. A field survey of roadside soil and plants in central Utah revealed that soil manganese concentrations in high traffic areas were up to 100-fold higher than historic lead levels. Soil manganese concentrations were highly correlated with distance from the roadway. In addition, roadside aquatic plants were higher in leaf tissue manganese than herbs or grasses. Submerged and emergent aquatic plants were sensitive bioindicators of manganese contamination. Manganese concentrations in soil and in some plant species along impacted roadsides often exceeded levels known to cause toxicity. We conclude that roadside soil and plants were apparently contaminated by manganese oxides from Mn-containing motor vehicle exhaust.

Manganese is an essential micronutrient for many organisms. Because of its unique role in the water oxidizing activity of photosystem II, manganese is required for photosynthetic growth in plants and cyanobacteria. Here we report on the mechanism of manganese uptake in the cyanobacterium Synechocystis sp. PCC 6803. Cells grown in 9 microM manganese-containing medium accumulate up to 1 x 10(8) manganese atoms/cell, bound to the outer membrane (pool A). This pool could be released by EDTA treatment. Accumulation of manganese in pool A was energized by photosynthetic electron flow. Moreover, collapsing the membrane potential resulted in the immediate release of this manganese pool. The manganese in this pool is mainly Mn(II) in a six-coordinate distorted environment. A distinctly different pool of manganese, pool B ( approximately 1.5 x 10(6) atoms/cell), could not be extracted by EDTA. Transport into pool B was light-independent and could be detected only under limiting manganese concentrations (1 nM). Evidently, manganese uptake in Synechocystis 6803 cells occurs in two steps. First, manganese accumulates in the outer membrane (pool A) in a membrane potential-dependent process. Next, manganese is transported through the inner membrane into pool B. We propose that pool A serves as a store that allows the cells to overcome transient limitations in manganese in the environment. PMID:12475258

Magnetotactic bacteria produce either magnetite (Fe(3)O(4)) or greigite (Fe(3)S(4)) crystals in cytoplasmic organelles called magnetosomes. Whereas greigite magnetosomes can contain up to 10 atom% copper, magnetite produced by magnetotactic bacteria was considered chemically pure for a long time and this characteristic was used to distinguish between biogenic and abiogenic crystals. Recently, it was shown that magnetosomes containing cobalt could be produced by three strains of Magnetospirillum. Here we show that magnetite crystals produced by uncultured magnetotactic bacteria can incorporate manganese up to 2.8 atom% of the total metal content (Fe+Mn) when manganese chloride is added to microcosms. Thus, chemical purity can no longer be taken as a strict prerequisite to consider magnetite crystals to be of biogenic origin. PMID:19187208

Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves, and methods of making, are disclosed. A single crystal ultra-long nanowire includes an ordered porous manganese oxide-based octahedral molecular sieve, and has an average length greater than about 10 micrometers and an average diameter of about 5 nanometers to about 100 nanometers. A film comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is stacked on a surface of a substrate, wherein the nanowires of each layer are substantially axially aligned. A free standing membrane comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is aggregately stacked, and wherein the nanowires of each layer are substantially axially aligned.

Magnetic resonance imaging (MRI) is an excellent non-invasive tool to investigate biological systems. The administration of the paramagnetic divalent ion manganese (Mn2+) enhances MRI contrast in vivo. Due to similarities between Mn2+ and calcium (Ca2+), the premise of manganese-enhanced MRI (MEMRI) is that the former may enter neurons and other excitable cells through voltage-gated Ca2+ channels. As such, MEMRI has been used to trace neuronal pathways, define morphological boundaries, and study connectivity in morphological and functional imaging studies. In this article, we provide a brief overview of MEMRI and discuss recently published data to illustrate the usefulness of this method, particularly in animal models. PMID:26217304

Manganese-Enhanced Magnetic Resonance Imaging (MEMRI) has proven itself to be a beneficial technique in the field of Neuroscience. This thesis applies MEMRI to studies in neuroscience by first establishing the limitations concerning the use of MEMRI in live rats. Experiment 1 used an osmotic pump for manganese (Mn) delivery to the lateral ventricles for acquisition of anatomical images using MEMRI. From my knowledge, this was the first method demonstrating slow infusion of Mn to the lateral ventricles. In Experiment 2, MEMRI was used for volumetric analysis the whole brain and hippocampus of prenatally stressed rats. To my knowledge, this study was the first to investigate the effect of generational prenatal stress on the structure of a rat's brain using MEMRI and histology. Additionally, Experiment 2 investigated the use of a subcutaneous osmotic pump to deliver Mn for MEMRI. A summary on the use of MEMRI in Neuroscience concludes this thesis, with a discussion on the methods used and related technical considerations.

First-principle electronic structure calculations for cadmium sulphide (CdS) sheet in hexagonal phase, with Manganese substitution and addition, as well as including the Cd defects, are investigated. The lattice constants calculated for CdS sheet agrees fairly well with results reported for thin films experimentally. The calculations of total spin density of states and partial density of states in different cases shows substantial magnetic dipole moments acquired by the sheet. A magnetic dipole moment 5.00612 μ{sub B} and band gap of the order 1 eV are found when cadmium atom is replaced by Manganese. The magnetism acquired by the sheet makes it functionally important candidate in many applications.

This invention encompasses methods of preserving protein function by contacting a protein with a composition comprising one or more purine or pyrimidine nucleosides (such as e.g., adenosine or uridine) and an antioxidant (such as e.g., manganese). In addition, the invention encompasses methods of treating and/or preventing a side effect of radiation exposure and methods of preventing a side effect of radiotherapy comprising administration of a pharmaceutically effective amount of a composition comprising one or more purine or pyrimidine nucleosides (such as e.g., adenosine or uridine) and an antioxidant (such as e.g., manganese) to a subject in need thereof. The compositions may comprise D. radiodurans extracts.